TWI586673B - Cross-linkable iridium complexes and organic light-emitting devices using the same - Google Patents
Cross-linkable iridium complexes and organic light-emitting devices using the same Download PDFInfo
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本發明係關於有機發光裝置(OLED)，且更特定言之係關於使用某些金屬錯合物之有機發光裝置。 The present invention relates to organic light-emitting devices (OLEDs), and more particularly to organic light-emitting devices using certain metal complexes.
出於許多原因，愈發需要利用有機材料之光電裝置。許多用於製造該等裝置之材料相對廉價，因此有機光電裝置具有超越無機裝置之成本優勢潛能。此外，有機材料之固有特性(諸如其可撓性)可使其極其適於特定應用，諸如製造可撓性基板。有機光電裝置之實例包括有機發光裝置(OLED)、有機光電晶體、有機光電電池及有機光偵測器。對於OLED而言，有機材料可具有超越習知材料之效能優勢。舉例而言，有機發射層發光之波長通常可易於以適當摻雜劑來調節。 Optoelectronic devices utilizing organic materials are increasingly needed for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, and thus organic optoelectronic devices have the potential to exceed the cost advantages of inorganic devices. Furthermore, the inherent properties of the organic material, such as its flexibility, can make it extremely suitable for a particular application, such as making a flexible substrate. Examples of organic optoelectronic devices include organic light-emitting devices (OLEDs), organic optoelectronic crystals, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials. For example, the wavelength at which the organic emissive layer emits light can generally be readily adjusted with appropriate dopants.
如本文中所用，術語"有機物"包括可用以製造有機光電裝置之聚合材料以及小分子有機材料。"小分子"係指並非聚合物之任何有機材料，且"小分子"實際上可相當大。在某些情況下小分子可包括重複單元。舉例而言，使用長鏈烷基作為取代基並不使分子自"小分子"類剔除。小分子亦可(例如)作為聚合物主鏈上之側基或作為主鏈之部分併入聚合物中。小分子亦可充當由在核心部分上構建之一系列化學殼組成之樹枝狀聚合物的核心部分。樹枝狀聚合物之核心部分可為螢光或磷光小分子發射體。樹枝狀聚合物可為"小分子"，且咸信目前用於 OLED領域之所有樹枝狀聚合物均為小分子。一般而言，小分子具有定義明確之具有單一分子量之化學式，而聚合物具有各分子間可不同之化學式及分子量。如本文中所用，"有機物"包括烴基及經雜原子取代之烴基配位子的金屬錯合物。 As used herein, the term "organic" includes polymeric materials and small molecular organic materials that can be used to make organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecules" can actually be quite large. In some cases small molecules may include repeating units. For example, the use of a long chain alkyl group as a substituent does not allow the molecule to be rejected from the "small molecule" class. Small molecules can also be incorporated into the polymer, for example, as pendant groups on the polymer backbone or as part of the backbone. Small molecules can also serve as a core part of a dendrimer composed of a series of chemical shells built on the core. The core portion of the dendrimer can be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be "small molecules" and are currently used All dendrimers in the OLED field are small molecules. In general, small molecules have well-defined chemical formulas with a single molecular weight, while polymers have different chemical formulas and molecular weights between molecules. As used herein, "organic" includes metal complexes of hydrocarbyl and heteroatom-substituted hydrocarbyl ligands.
OLED利用當橫過裝置施加電壓時發光之有機薄膜。OLED正成為適用於諸如平板顯示器、照明及背光之應用的愈發受關注技術。美國專利第5,844,363號、第6,303,238號及第5,707,745號中描述若干種OLED材料及組態，該等專利係以引用的方式全部併入本文中。 OLEDs utilize an organic film that illuminates when a voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for applications such as flat panel displays, lighting and backlighting. Several OLED materials and configurations are described in U.S. Patent Nos. 5,844,363, 6, 303, 238, and 5, 707, 745, each incorporated herein by reference.
OLED裝置通常(而並非總是)意欲經由至少一個電極發光，且一或多個透明電極可適用於有機光電裝置。舉例而言，諸如氧化銦錫(ITO)之透明電極材料可用作底部電極。亦可使用諸如美國專利第5,703,436號及第5,707,745號中揭示者之透明頂部電極，該等專利係以引用的方式全部併入。對於意欲僅經由底部電極發光之裝置而言，頂部電極無需透明且可由具有高電導率之厚且反射性金屬層組成。類似地，對於意欲僅經由頂部電極發光之裝置而言，底部電極可為不透明及/或反射性的。當電極無需透明時，使用較厚層可提供較佳之電導率，且使用反射性電極可藉由朝向透明電極反射光而增加經由另一電極發射之光的量。亦可製造完全透明裝置，其中兩個電極均為透明的。亦可製造側面發射OLED，且該等裝置中之一個或兩個電極均可為不透明或反射性的。 OLED devices are typically, but not always, intended to emit light via at least one electrode, and one or more transparent electrodes may be suitable for use in an organic optoelectronic device. For example, a transparent electrode material such as indium tin oxide (ITO) can be used as the bottom electrode. Transparent top electrodes such as those disclosed in U.S. Patent Nos. 5,703,436 and 5,707,745 are incorporated herein by reference. For devices intended to emit light only via the bottom electrode, the top electrode need not be transparent and may be composed of a thick and reflective metal layer with high electrical conductivity. Similarly, for devices intended to emit light only through the top electrode, the bottom electrode can be opaque and/or reflective. The use of a thicker layer provides better conductivity when the electrode does not need to be transparent, and the use of a reflective electrode can increase the amount of light emitted through the other electrode by reflecting light toward the transparent electrode. It is also possible to manufacture a completely transparent device in which both electrodes are transparent. Side-emitting OLEDs can also be fabricated, and one or both of the electrodes can be opaque or reflective.
如本文中所用，"頂部"意謂距離基板最遠，而"底部"意謂距離基板最近。舉例而言，對於具有兩個電極之裝置而言，底部電極為距離基板最近之電極且通常為所製造之第一電極。底部電極具有兩個表面，下表面距離基板最近且上表面稍遠離基板。當將第一層描述為"安置於"第二層上時，第一層稍遠離基板安置。除非說明第一層與第二層"實體接觸"，否則在第一與第二層之間可存在其他層。舉例而 言，可將陰極描述為"安置於"陽極上，即使其間存在各種有機層。 As used herein, "top" means the farthest from the substrate, and "bottom" means the closest to the substrate. For example, for a device having two electrodes, the bottom electrode is the electrode closest to the substrate and is typically the first electrode fabricated. The bottom electrode has two surfaces, the lower surface being closest to the substrate and the upper surface being slightly away from the substrate. When the first layer is described as being "placed on" the second layer, the first layer is placed slightly away from the substrate. Other layers may be present between the first and second layers unless the first layer is "physically contacted" with the second layer. For example In other words, the cathode can be described as being "placed on" the anode even if various organic layers are present therebetween.
如本文中所用，"可溶液處理"意謂能夠以溶液或懸浮液形式在液體介質中溶解、分散或傳輸及/或自液體介質沈積。 As used herein, "solution processable" means capable of being dissolved, dispersed or transported in a liquid medium in the form of a solution or suspension and/or deposited from a liquid medium.
如本文中所用且如熟習此項技術者通常將瞭解，若第一能級更接近真空能級，則第一"最高佔據分子軌道"(HOMO)或"最低未佔據分子軌道"(LUMO)能級係"大於"或"高於"第二HOMO或LUMO能級。由於相對於真空能級量測電離電位(IP)為負能量，因此較高之HOMO能級對應於具有較小絕對值之IP(負值較小之IP)。類似地，較高之LUMO能級對應於具有較小絕對值之電子親和力(EA)(負值較小之EA)。在習知能級圖(其中真空能級位於頂部)上，材料之LUMO能級高於相同材料之HOMO能級。"較高"之HOMO或LUMO能級似乎比"較低"之HOMO或LUMO能級更接近該圖之頂部。 As used herein and as generally understood by those skilled in the art, the first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy can be understood if the first energy level is closer to the vacuum level. The grade is "greater than" or "higher" than the second HOMO or LUMO energy level. Since the ionization potential (IP) is measured as a negative energy with respect to the vacuum level, the higher HOMO level corresponds to an IP having a smaller absolute value (IP with a smaller negative value). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (EA with a lower negative value). On conventional energy level diagrams (where the vacuum level is at the top), the LUMO energy level of the material is higher than the HOMO energy level of the same material. The "higher" HOMO or LUMO energy level appears to be closer to the top of the figure than the "lower" HOMO or LUMO energy level.
在一態樣中，本發明提供一種有機發光裝置，其包含：一第一電極；一第二電極；一安置於第一電極與第二電極之間的第一有機層，其中第一有機層為非電致發光的且其中第一有機層包含交聯金屬錯合物；及一安置於第一電極與第二電極之間的第二有機層，其中第二有機層為發射性的且其中第二有機層包含電致發光有機材料。在某些情況下，第一有機層另外包含摻雜劑。 In one aspect, the present invention provides an organic light-emitting device comprising: a first electrode; a second electrode; a first organic layer disposed between the first electrode and the second electrode, wherein the first organic layer Is non-electroluminescent and wherein the first organic layer comprises a crosslinked metal complex; and a second organic layer disposed between the first electrode and the second electrode, wherein the second organic layer is emissive and wherein The second organic layer comprises an electroluminescent organic material. In some cases, the first organic layer additionally contains a dopant.
在某些情況下，藉由使具有下式之可交聯銥錯合物交聯來形成交聯金屬錯合物：
其中L為與銥配位之配位子；其中A及B各自為5或6員芳環，且其中A-B表示經由環A上之氮原子及環B上之sp2混成化碳原子與銥配位之芳環鍵結對；其中變數"n"具有1-3之整數值；其中X為碳或氮原子；「而變數"a"具有1-5之整數值；其中S為包括一或多個各自獨立地選自由以下各基組成之群的鍵聯單元之間隔基：伸烷基、伸雜烷基、伸芳基、伸雜芳基、硼烷、醚、酯、胺、亞胺、醯胺、醯亞胺、硫醚及膦；且其中環A及B各自視情況分別經基團R1及R2取代，其中R1及R2各自表示一或多個位於其個別環之任意位置的獨立選擇取代基，其中取代基各自與其個別環稠合或鍵聯，且其中取代基各自獨立地選自由以下各基組成之群：烷基、雜烷基、芳基及雜芳基。 Wherein L is a coordinator coordinated to ruthenium; wherein A and B are each a 5- or 6-membered aromatic ring, and wherein AB represents a carbon atom via ring nitrogen and a sp 2 mixed carbon atom on ring B a position of an aromatic ring bond; wherein the variable "n" has an integer value of 1-3; wherein X is a carbon or nitrogen atom; "and the variable "a" has an integer value of 1-5; wherein S is one or more Spacers each independently selected from the group of bonding units consisting of alkyl, alkyl, aryl, heteroaryl, borane, ether, ester, amine, imine, hydrazine An amine, a quinone imine, a thioether, and a phosphine; and wherein each of the rings A and B is optionally substituted with a group R 1 and R 2 , respectively, wherein R 1 and R 2 each represent one or more positions at their individual rings The substituents are independently selected wherein the substituents are each fused or bonded to their individual rings, and wherein the substituents are each independently selected from the group consisting of alkyl, heteroalkyl, aryl and heteroaryl.
在另一態樣中，本發明提供一種製造有機發光裝置之方法，其包含：提供一安置於一基板上之第一電極；藉由使可交聯金屬錯合物經溶液沈積於第一電極上且使該可交聯金屬錯合物交聯而形成一第一有機層；在第一電極上形成一第二有機層，其中第二有機層包含有機電致發光材料；且形成一安置於第一及第二有機層上之第二電極。在某些情況下，用於使可交聯金屬錯合物溶液沈積之溶液另外包含摻雜 劑。 In another aspect, the present invention provides a method of fabricating an organic light-emitting device, comprising: providing a first electrode disposed on a substrate; and depositing a crosslinkable metal complex on the first electrode by solution And crosslinking the crosslinkable metal complex to form a first organic layer; forming a second organic layer on the first electrode, wherein the second organic layer comprises an organic electroluminescent material; and forming a a second electrode on the first and second organic layers. In some cases, the solution used to deposit the crosslinkable metal complex solution additionally contains doping Agent.
在另一態樣中，本發明提供一種具有下式之銥錯合物：
其中L為與銥配位之配位子；其中A及B各自為5或6員芳環，且其中A-B表示經由環A上之氮原子及環B上之sp2混成化碳原子與銥配位之芳環鍵結對；其中變數"n"具有1-3之數值；其中P為可聚合基團，而變數"a"具有1-5之整數值；其中S為含有胺基之間隔基；且其中環A及B各自視情況分別經基團R1及R2取代，其中R1及R2各自表示一或多個取代基，其中該或該等取代基各自位於其個別環之任意位置，其中取代基各自相同或不同，其中取代基各自與其個別環稠合或鍵聯，且其中取代基各自獨立地選自由以下各基組成之群：烷基、雜烷基、芳基及雜芳基。 Wherein L is a coordinator coordinated to ruthenium; wherein A and B are each a 5- or 6-membered aromatic ring, and wherein AB represents a carbon atom via ring nitrogen and a sp 2 mixed carbon atom on ring B a position of an aromatic ring bond; wherein the variable "n" has a value of 1-3; wherein P is a polymerizable group, and the variable "a" has an integer value of 1-5; wherein S is a spacer containing an amine group; And wherein each of the rings A and B is optionally substituted with a group R 1 and R 2 , respectively, wherein R 1 and R 2 each represent one or more substituents, wherein the or each substituent is located at any position of its individual ring Wherein the substituents are each the same or different, wherein the substituents are each fused or bonded to their respective rings, and wherein the substituents are each independently selected from the group consisting of alkyl, heteroalkyl, aryl and heteroaryl base.
在另一態樣中，本發明提供一種有機發光裝置，其包含：一第一電極；一第二電極；及一包含共價交聯基質之第一有機層，其中該交聯基質包含銥錯合物。在某些情況下，第一有機層另外包含摻雜劑。 In another aspect, the present invention provides an organic light-emitting device comprising: a first electrode; a second electrode; and a first organic layer comprising a covalently crosslinked matrix, wherein the crosslinked matrix comprises Compound. In some cases, the first organic layer additionally contains a dopant.
100‧‧‧有機發光裝置 100‧‧‧Organic lighting device
110‧‧‧基板 110‧‧‧Substrate
115‧‧‧陽極 115‧‧‧Anode
120‧‧‧電洞注入層 120‧‧‧ hole injection layer
125‧‧‧電洞傳輸層 125‧‧‧ hole transport layer
130‧‧‧電子阻擋層 130‧‧‧Electronic barrier
135‧‧‧發射層 135‧‧‧ emission layer
140‧‧‧電洞阻擋層 140‧‧‧ hole barrier
145‧‧‧電子傳輸層 145‧‧‧Electronic transport layer
150‧‧‧電子注入層 150‧‧‧electron injection layer
155‧‧‧保護層 155‧‧‧Protective layer
160‧‧‧陰極/有機保護層 160‧‧‧Cathode/Organic Protective Layer
162‧‧‧第一導電層/薄金屬層 162‧‧‧First conductive layer/thin metal layer
164‧‧‧第二導電層/較厚導電金屬氧化物層 164‧‧‧Second Conductive Layer/Thicker Conductive Metal Oxide Layer
200‧‧‧倒置型OLED 200‧‧‧Inverted OLED
210‧‧‧基板 210‧‧‧Substrate
215‧‧‧陰極 215‧‧‧ cathode
220‧‧‧發射層 220‧‧‧Emission layer
225‧‧‧電洞傳輸層 225‧‧‧ hole transport layer
230‧‧‧陽極 230‧‧‧Anode
圖1展示具有獨立電子傳輸、電洞傳輸及發射層以及其他層之有機發光裝置。 Figure 1 shows an organic light emitting device having separate electron transport, hole transport and emissive layers, and other layers.
圖2展示不具有獨立電子傳輸層之倒置型有機發光裝置。 Figure 2 shows an inverted organic light-emitting device without an independent electron transport layer.
圖3展示用於實例1與比較實例1之裝置的架構。 3 shows the architecture of the apparatus for Example 1 and Comparative Example 1.
圖4展示對於實例1及比較實例1之裝置而言，電流密度作為電壓函數之曲線。 Figure 4 shows a plot of current density as a function of voltage for the devices of Example 1 and Comparative Example 1.
圖5展示對於實例1及比較實例1之裝置而言，亮度作為電壓函數之曲線。 Figure 5 shows a plot of brightness as a function of voltage for the devices of Example 1 and Comparative Example 1.
圖6展示描述為發光效率對亮度之曲線的實例1及比較實例1之裝置的電流效率。 6 shows the current efficiencies of the devices of Example 1 and Comparative Example 1 described as a plot of luminous efficiency versus brightness.
圖7展示描述為發光強度對時間之曲線的實例1及比較實例1之裝置的運作壽命。 Figure 7 shows the operational life of the apparatus of Example 1 and Comparative Example 1 described as a plot of luminous intensity versus time.
圖8展示實例2之裝置所產生之電致發光光譜。 Figure 8 shows the electroluminescence spectrum produced by the apparatus of Example 2.
圖9展示實例2之裝置的電流-電壓-亮度曲線。 Figure 9 shows the current-voltage-luminance curve of the device of Example 2.
圖10展示描述為發光效率對亮度之曲線的實例2之裝置的電流效率。 Figure 10 shows the current efficiency of the device of Example 2 depicted as a plot of luminous efficiency versus brightness.
圖11展示對於實例3及4之裝置而言，電流密度作為電壓函數之曲線。 Figure 11 shows the current density as a function of voltage for the devices of Examples 3 and 4.
圖12展示對於實例3及4之裝置而言，亮度作為電壓函數之曲線。 Figure 12 shows a plot of brightness as a function of voltage for the devices of Examples 3 and 4.
圖13展示描述為發光效率對亮度之曲線的實例3及4之裝置的電流效率曲線。 Figure 13 shows current efficiency curves for the devices of Examples 3 and 4 depicted as a plot of luminous efficiency versus brightness.
圖14展示對於實例5、6及7之裝置而言，電流密度作為電壓函數之曲線。 Figure 14 shows a plot of current density as a function of voltage for the devices of Examples 5, 6 and 7.
圖15展示描述為發光效率對亮度之曲線的實例5、6及7之裝置的電流效率曲線。 Figure 15 shows current efficiency curves for the devices of Examples 5, 6 and 7 depicted as a plot of luminous efficiency versus brightness.
圖16展示描述為發光強度對時間之曲線的實例5、6及7之裝置的運作壽命。 Figure 16 shows the operational life of the devices of Examples 5, 6 and 7 depicted as a plot of luminous intensity versus time.
通常，OLED包含至少一個安置於陽極與陰極之間且與其電連接之有機層。當施加電流時，陽極向有機層中注入電洞且陰極向有機層中注入電子。所注入之電洞及電子各自向相反帶電電極遷移。當電子及電洞定位於相同分子上時，形成作為具有激發能態之定域電子電洞對的"激子"。當激子經由光電發射機制弛豫時發光。在某些情況下，激子可定位於準分子或激發複合物體上。亦可存在諸如熱弛豫之非輻射機制，但通常認為其不當。 Typically, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects a hole into the organic layer and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the opposite charged electrode. When electrons and holes are positioned on the same molecule, an "exciton" is formed as a pair of localized electron holes having an excited energy state. The exciton emits light when it relaxes via a photoemission mechanism. In some cases, excitons can be localized on excimer or excited composite objects. Non-radiative mechanisms such as thermal relaxation may also exist, but are generally considered to be improper.
如(例如)美國專利第4,769,292號中所揭示，初始OLED使用自其單重態("螢光")發光之發射分子，該專利係以引用的方式全部併入。螢光發射通常發生在小於10奈秒之時段中。 The initial OLED uses an emissive molecule that emits light from its singlet state ("fluorescent"), as disclosed in, for example, U.S. Patent No. 4,769,292, the disclosure of which is incorporated herein in its entirety. Fluorescence emissions typically occur in periods of less than 10 nanoseconds.
近來，已證明具有自三重態("磷光")發光之發射材料的OLED。Baldo等人，"Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature，第395卷，151-154,1998；("Baldo-I")及Baldo等人，"Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl.Phys.Lett.，第75卷，第1期，4-6(1999)("Baldo-II")，其係以引用的方式全部併入。磷光可稱為"禁戒"躍遷，此係因為躍遷要求自旋態變化，且量子力學指示該躍遷不利。因此，磷光通常發生在超過至少10奈秒、且通常大於100奈秒之時段中。若磷光之自然輻射壽命過長，則三重態可藉由非輻射機制衰減以使得不發光。在極低溫度下，在含有具有非共用電子對的雜原子之分子中亦常觀察到有機磷光。2,2'-聯吡啶為此種分子。非輻射衰減機制通常具有溫度依賴性，使得在液氮溫度下顯示磷光之有機材料在室溫下通常不顯示磷光。但如Baldo所證明，此問 題可藉由選擇在室溫下發出磷光之磷光化合物來解決。代表性發射層包括摻雜或未摻雜之磷光有機金屬材料，諸如美國專利第6,303,238號及第6,310,360號；美國專利申請公開案第2002-0034656號；第2002-0182441號；第2003-0072964號；及WO-02/074015中所揭示。 Recently, OLEDs having emission materials derived from triplet ("phosphorescence") luminescence have been demonstrated. Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, Vol. 395, 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices" Based on electrophosphorescence, "Appl. Phys. Lett., Vol. 75, No. 1, 4-6 (1999) ("Baldo-II"), which is incorporated by reference in its entirety. Phosphorescence can be called a "forbidden" transition, because the transition requires a spin state change, and quantum mechanics indicates that the transition is unfavorable. Thus, phosphorescence typically occurs in periods of more than at least 10 nanoseconds, and typically greater than 100 nanoseconds. If the natural radiation lifetime of phosphorescence is too long, the triplet state can be attenuated by a non-radiative mechanism so that it does not emit light. At very low temperatures, organic phosphorescence is also often observed in molecules containing heteroatoms with unshared electron pairs. 2,2'-bipyridyl is such a molecule. Non-radiative decay mechanisms are typically temperature dependent such that organic materials that exhibit phosphorescence at liquid nitrogen temperatures typically do not exhibit phosphorescence at room temperature. But as Baldo proved, this question The problem can be solved by selecting a phosphorescent compound that emits phosphorescence at room temperature. Representative emissive layers include doped or undoped phosphorescent organometallic materials, such as U.S. Patent Nos. 6,303,238 and 6,310,360; U.S. Patent Application Publication No. 2002-0034656; No. 2002-0182441; No. 2003-0072964 ; and as disclosed in WO-02/074015.
通常，咸信OLED中之激子以約3：1，亦即約75%三重態及25%單重態之比率產生。參見Adachi等人，"Nearly 100% Internal Phosphorescent Efficiency In An Organic Light Emitting Device," J.Appl.Phys.,90,5048(2001)，其係以引用的方式全部併入。在許多情況下，單重態激子可易於經由"系統間跨越"將其能量轉移至三重激發態，而三重態激子可不易於將其能量轉移至單重激發態。因此，磷光OLED在理論上可能具有100%之內部量子效率。在螢光裝置中，三重態激子之能量通常喪失於加熱裝置之無輻射衰減過程，導致低得多之內部量子效率。舉例而言，美國專利第6,303,238號中揭示使用自三重激發態發射之磷光材料的OLED，該專利係以引用的方式全部併入。 Typically, excitons in the OLED are produced at a ratio of about 3:1, i.e., about 75% triplet and 25% singlet. See Adachi et al., "Nearly 100% Internal Phosphorescent Efficiency In An Organic Light Emitting Device," J. Appl. Phys., 90, 5048 (2001), which is incorporated by reference in its entirety. In many cases, singlet excitons can easily transfer their energy to a triplet excited state via "intersystem crossings", while triplet excitons may not readily transfer their energy to a singlet excited state. Therefore, phosphorescent OLEDs may theoretically have an internal quantum efficiency of 100%. In fluorescent devices, the energy of the triplet excitons is typically lost to the non-radiative decay process of the heating device, resulting in much lower internal quantum efficiency. An OLED using a phosphorescent material that emits from a triplet excited state is disclosed, for example, in U.S. Patent No. 6,303,238, the disclosure of which is incorporated herein by reference.
三重激發態至中間非三重態(由此發生發射衰減)之躍遷後可發出磷光。舉例而言，與鑭系元素配位之有機分子常自定位於鑭系金屬上之激發態發出磷光。然而，該等材料並不直接自三重激發態發出磷光，而改為自集中於鑭系金屬離子上之原子激發態發射。二酮化銪錯合物說明一組此等類型之物質。 Phosphorescence can be emitted after a transition from a triplet excited state to an intermediate non-triplet state (from which emission decay occurs). For example, organic molecules coordinated to lanthanides often emit phosphorescence from an excited state localized on a lanthanide metal. However, these materials do not directly emit phosphorescence from the triplet excited state, but instead concentrate on the atomic excited state emission on the lanthanide metal ion. The diketone ruthenium complex describes a group of these types of materials.
藉由限制，較佳經由鍵結極其接近高原子序數之原子的有機分子可使來自三重態之磷光增強超過螢光。此稱為重原子效應之現象係由稱為自旋軌道耦合之機制而產生。可自諸如參(2-苯基吡啶)銥(III)之有機金屬分子的激發金屬至配位子電荷轉移(MLCT)狀態觀察到該磷光躍遷。 By limitation, it is preferred that the phosphorescence from the triplet state be enhanced beyond fluorescence by organic molecules that are bonded to atoms that are very close to the high atomic number. This phenomenon, called the heavy atom effect, is produced by a mechanism called spin-orbit coupling. The phosphorescence transition can be observed from the excited metal to the ligand charge transfer (MLCT) state of an organometallic molecule such as ginseng (2-phenylpyridine) ruthenium (III).
如本文中所用，術語"三重態能量"係指對應於在給定材料之磷光光譜中可辨別之最高能量特徵的能量。最高能量特徵不必為在磷光光 譜中具有最大強度之峰，且可為(例如)該峰之高能量側上具有清晰肩部之局部最大值。 As used herein, the term "triplet energy" refers to the energy corresponding to the highest energy characteristic discernible in the phosphorescence spectrum of a given material. The highest energy characteristic does not have to be in phosphorescence The peak with the greatest intensity in the spectrum, and may be, for example, a local maximum with a sharp shoulder on the high energy side of the peak.
圖1展示有機發光裝置100。該等圖不必按比例繪製。裝置100可包括一基板110、一陽極115、一電洞注入層120、一電洞傳輸層125、一電子阻擋層130、一發射層135、一電洞阻擋層140、一電子傳輸層145、一電子注入層150、一保護層155及一陰極160。陰極160為一具有一第一導電層162及一第二導電層164之複合陰極。可藉由依次沈積所述層來製造裝置100。 FIG. 1 shows an organic light emitting device 100. The figures are not necessarily to scale. The device 100 can include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, and an electron transport layer 145. An electron injection layer 150, a protective layer 155 and a cathode 160. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by depositing the layers in sequence.
基板110可為提供所需結構特性之任何合適基板。基板110可為可撓性或剛性的。基板110可為透明、半透明或不透明的。塑料及玻璃為較佳剛性基板材料之實例。塑料及金屬箔為較佳可撓性基板材料之實例。基板110可為半導體材料以便製造電路。舉例而言，基板110可為於其上製造電路、能夠控制隨後沈積於基板上之OLED的矽晶圓。可使用其他基板。可選擇基板110之材料及厚度以獲得所需結構及光學特性。 Substrate 110 can be any suitable substrate that provides the desired structural characteristics. The substrate 110 can be flexible or rigid. Substrate 110 can be transparent, translucent or opaque. Plastics and glass are examples of preferred rigid substrate materials. Plastics and metal foils are examples of preferred flexible substrate materials. Substrate 110 can be a semiconductor material to make an electrical circuit. For example, the substrate 110 can be a germanium wafer on which an electrical circuit is fabricated that can control an OLED that is subsequently deposited on the substrate. Other substrates can be used. The material and thickness of the substrate 110 can be selected to achieve the desired structural and optical properties.
陽極115可為具有足夠電導性以將電洞傳輸至有機層之任何合適陽極。陽極115之材料較佳具有高於約4eV之功函數("高功函數材料")。較佳陽極材料包括導電金屬氧化物，諸如氧化銦錫(ITO)及氧化銦鋅(IZO)，氧化鋁鋅(AlZnO)及金屬。陽極115(及基板110)可足夠透明以產生底部發射裝置。較佳透明基板及陽極組合為沈積於玻璃或塑料(基板)上之市售ITO(陽極)。可撓性及透明基板-陽極組合揭示於美國專利第5,844,363號及第6,602,540 B2號中，其係以引用的方式全部併入。陽極115可為不透明及/或反射性的。對於某些頂部發射裝置而言，反射陽極115可為較佳以增加自裝置頂部發射之光的量。可選擇陽極115之材料及厚度以獲得所需導電性及光學特性。若陽極115為透明的，則對於特定材料而言可能存在足夠厚以提供所需電導率，而足 夠薄以提供所需透明度之厚度範圍。可使用其他陽極材料及結構。 The anode 115 can be any suitable anode that has sufficient electrical conductivity to transport holes to the organic layer. The material of the anode 115 preferably has a work function ("high work function material") above about 4 eV. Preferred anode materials include conductive metal oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals. The anode 115 (and substrate 110) can be sufficiently transparent to create a bottom emitting device. Preferably, the transparent substrate and the anode are combined as a commercially available ITO (anode) deposited on glass or plastic (substrate). The flexible and transparent substrate-anode combination is disclosed in U.S. Patent Nos. 5,844,363 and 6,602,540 B2, all incorporated herein by reference. The anode 115 can be opaque and/or reflective. For some top emitting devices, reflective anode 115 can be preferably used to increase the amount of light emitted from the top of the device. The material and thickness of the anode 115 can be selected to achieve the desired conductivity and optical properties. If the anode 115 is transparent, it may be thick enough for a particular material to provide the desired conductivity, while Thin enough to provide the desired range of transparency. Other anode materials and structures can be used.
電洞傳輸層125可包括能夠傳輸電洞之材料。電洞傳輸層130可為本徵的(未摻雜的)或經摻雜的。摻雜可用以增強電導率。α-NPD及TPD為本徵電洞傳輸層之實例。p摻雜電洞傳輸層之實例為如Forrest等人之美國專利申請公開案第2003-0230980號中所揭示以50：1之莫耳比摻雜有F4-TCNQ之m-MTDATA，該專利係以引用的方式全部併入。可使用其他電洞傳輸層。 The hole transport layer 125 can include a material capable of transporting holes. The hole transport layer 130 can be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of α-NPD and TPD intrinsic hole transport layers. An example of a p-doped hole transport layer is m-MTDATA doped with F 4 -TCNQ at a molar ratio of 50:1 as disclosed in US Patent Application Publication No. 2003-0230980 to Forrest et al. It is incorporated by reference in its entirety. Other hole transport layers can be used.
發射層135可包括當電流在陽極115與陰極160之間穿過時能夠發光之有機材料。較佳地，發射層135含有磷光發射材料，儘管亦可使用螢光發射材料。磷光材料由於與該等材料相關之較高發光效率而為較佳。發射層135亦可包含能夠傳輸電子及/或電洞、摻雜有可捕獲電子、電洞及/或激子以使得激子經由光電發射機制自發射性材料弛豫之發射性材料的主體材料。發射層135可包含組合傳輸及發射特性之單一材料。無論發射性材料係為摻雜劑或主要成份，發射層135均可包含其他材料，諸如調節發射性材料之發射的摻雜劑。發射層135可包括複數種能夠組合發射所需光譜之發射性材料。磷光發射性材料之實例包括Ir(ppy)3。螢光發射性材料之實例包括DCM及DMQA。主體材料之實例包括Alq3、CBP及mCP。發射性材料及主體材料之實例揭示於Thompson等人之美國專利第6,303,238號中，該專利係以引用的方式全部併入。發射性材料可以多種方式包括於發射層135中。舉例而言，可將發射性小分子併入聚合物中。此可藉由數種方式來實現：將小分子以獨立且不同之分子物質形式摻雜至聚合物中；或將小分子併入聚合物之主鏈中以便形成共聚物；或將小分子作為側基鍵結於聚合物上。可使用其他發射層材料及結構。舉例而言，可提供小分子發射性材料作為樹枝狀聚合物之核心。 The emissive layer 135 can include an organic material that is capable of emitting light when current is passed between the anode 115 and the cathode 160. Preferably, the emissive layer 135 contains a phosphorescent emissive material, although a fluorescent emissive material can also be used. Phosphorescent materials are preferred due to the higher luminous efficiency associated with such materials. The emissive layer 135 may also comprise a host material capable of transporting electrons and/or holes, doped with trappable electrons, holes and/or excitons to cause excitons to relax from the emissive material via a photoemissive mechanism. . Emissive layer 135 can comprise a single material that combines transmission and emission characteristics. Whether the emissive material is a dopant or a primary component, the emissive layer 135 can comprise other materials, such as dopants that modulate the emission of the emissive material. Emissive layer 135 can include a plurality of emissive materials capable of combining the desired spectra. Examples of the phosphorescent emissive material include Ir(ppy) 3 . Examples of fluorescent emissive materials include DCM and DMQA. Examples of the host material include Alq 3 , CBP, and mCP. Examples of emissive materials and host materials are disclosed in U.S. Patent No. 6,303,238, the entire disclosure of which is incorporated herein by reference. The emissive material can be included in the emissive layer 135 in a variety of ways. For example, emissive small molecules can be incorporated into the polymer. This can be achieved in several ways: by doping small molecules into the polymer as separate and distinct molecular species; or by incorporating small molecules into the backbone of the polymer to form a copolymer; or using small molecules as The pendant groups are bonded to the polymer. Other emissive layer materials and structures can be used. For example, a small molecule emissive material can be provided as the core of the dendrimer.
許多適用之發射性材料包括一或多個與金屬中心結合之配位 子。若配位子直接促進有機金屬發射性材料之光活性特性，則配位子可被稱為"光活性"配位子。"光活性"配位子可結合金屬提供當發射光子時電子在其間移動之能級。其他配位子可稱為"輔助"配位子。輔助配位子可(例如)藉由使光活性配位子之能級移動來改變分子之光活性特性，但輔助配位子並不直接提供與光發射有關之能級。在一種分子中具有光活性之配位子在另一分子中可為輔助配位子。該等光活性及輔助之定義希望作為非限制性理論。 Many suitable emissive materials include one or more coordination sites with metal centers child. If the ligand directly promotes the photoactive properties of the organometallic emissive material, the ligand can be referred to as a "photoactive" ligand. A "photoactive" ligand can combine with a metal to provide an energy level at which electrons move between photons. Other ligands can be referred to as "auxiliary" ligands. Auxiliary ligands can, for example, alter the photoactive properties of a molecule by shifting the energy level of the photoactive ligand, but the ancillary ligand does not directly provide an energy level associated with light emission. A photoactive ligand in one molecule can be an auxiliary ligand in another molecule. The definition of such photoactivity and aids is intended as a non-limiting theory.
電子傳輸層145可包括能夠傳輸電子之材料。電子傳輸層145可為本徵的(未摻雜的)或經摻雜的。摻雜可用以增強電導率。Alq3為本徵電子傳輸層之實例。n摻雜電子傳輸層之實例為如Forrest等人之美國專利申請公開案第2003-0230980號所揭示以1：1之莫耳比摻雜有Li之BPhen，該專利係以引用的方式全部併入。可使用其他電子傳輸層。 The electron transport layer 145 can include a material capable of transporting electrons. Electron transport layer 145 can be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. An example of an Alq 3 intrinsic electron transport layer. An example of an n-doped electron-transporting layer is BPhen, which is doped with Li at a molar ratio of 1:1 as disclosed in U.S. Patent Application Publication No. 2003-0230980, the entire disclosure of which is incorporated herein by reference. In. Other electron transport layers can be used.
可選擇電子傳輸層之電荷攜帶組份以使得電子可有效地自陰極注入電子傳輸層之LUMO(最低未佔據分子軌道)能級。"電荷攜帶組分"為造成實際上傳輸電子之LUMO能級的材料。此組份可為基底材料或其可為摻雜劑。有機材料之LUMO能級通常可由彼材料之電子親和力來表徵，且陰極之相對電子注入效率通常可依據陰極材料之功函數來表徵。此意謂可依據ETL之電荷攜帶組份之電子親和力及陰極材料之功函數來說明電子傳輸層及相鄰陰極之較佳特性。特定言之，為達成高電子注入效率，陰極材料之功函數較佳不比電子傳輸層之電荷攜帶組份的電子親和力高出約0.75eV以上、更佳至多約0.5eV。類似考慮因素適用於電子注入之任何層。 The charge carrying component of the electron transport layer can be selected such that electrons can be efficiently injected from the cathode into the LUMO (lowest unoccupied molecular orbital) level of the electron transport layer. The "charge carrying component" is a material that causes the LUMO energy level to actually transport electrons. This component can be a substrate material or it can be a dopant. The LUMO energy level of an organic material can generally be characterized by the electron affinity of the material, and the relative electron injection efficiency of the cathode can generally be characterized by the work function of the cathode material. This means that the preferred properties of the electron transport layer and adjacent cathodes can be explained by the electron affinity of the charge carrying component of the ETL and the work function of the cathode material. In particular, to achieve high electron injection efficiency, the work function of the cathode material is preferably no more than about 0.75 eV, more preferably up to about 0.5 eV, than the electron-affinity of the charge-carrying component of the electron transport layer. Similar considerations apply to any layer of electron injection.
陰極160可為此項技術已知之任何合適材料或材料組合，以使得陰極160能夠傳導電子且將其注入裝置100之有機層。陰極160可為透明或不透明的，且可為反射性的。金屬及金屬氧化物為合適陰極材料之實例。陰極160可為單一層或可具有複合結構。圖1展示具有薄金屬 層162及較厚導電金屬氧化物層164之複合陰極160。在複合陰極中，較厚層164之較佳材料包括ITO、IZO及此項技術中已知之其他材料。以引用的方式全部併入之美國專利第5,703,436號、第5,707,745號、第6,548,956 B2號及第6,576,134 B2號揭示包括具有諸如Mg：Ag之金屬薄層與上覆透明、導電、濺射沈積ITO層的複合陰極之陰極的實例。與下伏有機層接觸之陰極160之部分，無論其為單層陰極160、複合陰極之薄金屬層162或某些其他部分，其較佳由具有低於約4eV之功函數的材料("低功函數材料")製成。可使用其他陰極材料及結構。 Cathode 160 can be any suitable material or combination of materials known in the art to enable cathode 160 to conduct electrons and inject it into the organic layer of device 100. Cathode 160 can be transparent or opaque and can be reflective. Metals and metal oxides are examples of suitable cathode materials. Cathode 160 can be a single layer or can have a composite structure. Figure 1 shows a thin metal Layer 162 and composite cathode 160 of thicker conductive metal oxide layer 164. Among the composite cathodes, preferred materials for the thicker layer 164 include ITO, IZO, and other materials known in the art. U.S. Patent Nos. 5,703,436, 5,707,745, 6,548,956 B2, and 6,576,134 B2, the entire disclosures of which are incorporated herein by reference. An example of a cathode of a composite cathode. The portion of the cathode 160 that is in contact with the underlying organic layer, whether it is a single layer cathode 160, a thin metal layer 162 of a composite cathode, or some other portion, is preferably made of a material having a work function of less than about 4 eV ("low The work function material is made of "). Other cathode materials and structures can be used.
阻擋層可用以減少離開發射層之電荷載流子(電子或電洞)及/或激子之數目。電子阻擋層130可安置於發射層135與電洞傳輸層125之間以阻擋電子沿電洞傳輸層125之方向離開發射層135。類似地，電洞阻擋層140可安置於發射層135與電子傳輸層145之間以阻擋電洞沿電子傳輸層145之方向離開發射層135。阻擋層亦可用以阻擋激子自發射層向外擴散。Forrest等人之美國專利第6,097,147號及美國專利申請公開案第2003-0230980號中更詳細地描述關於阻擋層之理論及用途，該等專利係以引用的方式全部併入。 A barrier layer can be used to reduce the number of charge carriers (electrons or holes) and/or excitons exiting the emissive layer. The electron blocking layer 130 may be disposed between the emissive layer 135 and the hole transport layer 125 to block electrons from exiting the emissive layer 135 in the direction of the hole transport layer 125. Similarly, a hole blocking layer 140 may be disposed between the emissive layer 135 and the electron transport layer 145 to block the holes from exiting the emissive layer 135 in the direction of the electron transport layer 145. The barrier layer can also be used to block excitons from diffusing outward from the emissive layer. The theory and use of the barrier layer is described in more detail in U.S. Patent No. 6,097,147, issued to toS.
如本文中所用且如熟習此項技術者應瞭解，術語"阻擋層"意謂該層提供顯著抑制電荷載流子及/或激子經由裝置傳輸之障壁，而未表明該層必須完全阻擋電荷載流子及/或激子。與缺乏阻擋層之類似裝置相比，該阻擋層在裝置中之存在可產生實質上較高之效率。阻擋層亦可用以將發射限制於OLED之所需區域。 As used herein and as understood by those skilled in the art, the term "barrier layer" means that the layer provides a barrier that significantly inhibits the transport of charge carriers and/or excitons through the device, without indicating that the layer must completely block the charge. Carriers and/or excitons. The presence of the barrier layer in the device can result in substantially higher efficiencies compared to similar devices lacking a barrier layer. The barrier layer can also be used to limit emission to the desired area of the OLED.
通常，注入層由可改良電荷載流子自諸如電極或有機層之一層注入相鄰有機層之材料組成。注入層亦可執行電荷傳輸功能。在裝置100中，電洞注入層120可為改良電洞自陽極115注入電洞傳輸層125中之任何層。CuPc為可用作自ITO陽極115及其他陽極之電洞注入層的材料之實例。在裝置100中，電子注入層150可為改良電子注入電子傳 輸層145之任何層。LiF/Al為可用作自相鄰層進入電子傳輸層中之電子注入層的材料之實例。其他材料或材料組合可用於注入層。視特定裝置之組態而定，可將注入層安置在不同於裝置100中所示位置之位置。注入層之更多實例提供於Lu等人之美國專利申請案第09/931,948號中，其係以引用的方式全部併入。電洞注入層可包含溶液沈積材料，諸如旋塗聚合物，例如PEDOT：PSS，或其可為蒸氣沈積之小分子材料，例如CuPc或MTDATA。 Typically, the implant layer is comprised of a material that can improve the charge carriers from one of the layers of the electrode or organic layer to the adjacent organic layer. The injection layer can also perform a charge transfer function. In device 100, hole injection layer 120 can be an improved hole injected from anode 115 into any of the layers in hole transport layer 125. CuPc is an example of a material that can be used as a hole injection layer from the ITO anode 115 and other anodes. In the device 100, the electron injection layer 150 can be an improved electron injection electron transfer Any layer of the transfer layer 145. LiF/Al is an example of a material that can be used as an electron injecting layer that enters an electron transport layer from an adjacent layer. Other materials or combinations of materials can be used for the injection layer. Depending on the configuration of the particular device, the injection layer can be placed at a different location than that shown in device 100. Further examples of the injection layer are provided in U.S. Patent Application Serial No. 09/931,948, the entire disclosure of which is incorporated herein by reference. The hole injection layer may comprise a solution deposition material such as a spin-on polymer such as PEDOT:PSS, or it may be a vapor deposited small molecule material such as CuPc or MTDATA.
電洞注入層(HIL)可使陽極表面平坦化或潤濕以自陽極提供有效電洞注入電洞注入材料中。電洞注入層亦可具有電荷攜帶組份，其具有如本文所述之相對電離電位(IP)能量所界定，有利於與HIL一側上之相鄰陽極層及HIL對側上之電洞傳輸層匹配之HOMO(最高佔據分子軌道)能級。"電荷攜帶組份"為造成實際上傳輸電洞之HOMO能級的材料。此組份可為HIL之基底材料或其可為摻雜劑。使用摻雜HIL使得可選擇摻雜劑之電學特性且可選擇主體之形態特性，諸如潤濕、可撓性、韌性等。HIL材料之較佳特性使得電洞可自陽極有效地注入HIL材料中。特定言之，HIL之電荷攜帶組份較佳具有比陽極材料之IP高出至多約0.7eV之IP。更佳地，電荷攜帶組份具有比陽極材料大出至多約0.5eV之IP。類似考慮因素適用於電洞注入之任何層。HIL材料進一步區別於通常用於OLED之電洞傳輸層的習知電洞傳輸材料之處在於該等HIL材料可具有實質上小於習知電洞傳輸材料之電洞電導率的電洞電導率。本發明之HIL的厚度可足夠厚以有助於使陽極層之表面平坦化或潤濕。舉例而言，低至10nm之HIL厚度可為極平滑陽極表面所接受。然而，由於陽極表面趨向於極粗糙，因此在某些情況下可需要高達50nm之HIL厚度。 A hole injection layer (HIL) can planarize or wet the anode surface to provide effective holes into the hole injection material from the anode. The hole injection layer may also have a charge carrying component defined by the relative ionization potential (IP) energy as described herein to facilitate transmission of holes along the adjacent anode layer on the HIL side and on the opposite side of the HIL. The layer-matched HOMO (highest occupied molecular orbital) energy level. The "charge carrying component" is a material that causes the HOMO energy level to actually transmit a hole. This component can be a base material for the HIL or it can be a dopant. The use of doped HIL allows the electrical properties of the dopant to be selected and the morphological properties of the body such as wetting, flexibility, toughness, etc., to be selected. The preferred properties of the HIL material allow the holes to be efficiently injected into the HIL material from the anode. In particular, the charge carrying component of the HIL preferably has an IP that is at most about 0.7 eV higher than the IP of the anode material. More preferably, the charge carrying component has an IP that is up to about 0.5 eV greater than the anode material. Similar considerations apply to any layer of hole injection. The HIL material is further distinguished from conventional hole transport materials commonly used in hole transport layers of OLEDs in that the HIL materials can have a hole conductivity that is substantially smaller than the hole conductivity of a conventional hole transport material. The thickness of the HIL of the present invention may be thick enough to help planarize or wet the surface of the anode layer. For example, a HIL thickness as low as 10 nm can be accepted for an extremely smooth anode surface. However, since the anode surface tends to be extremely rough, a HIL thickness of up to 50 nm may be required in some cases.
保護層在後續製造方法期間可用以保護下伏層。舉例而言，用以製造金屬或金屬氧化物頂部電極之方法可損害有機層，且保護層可 用以減少或消除該損害。在裝置100中，保護層155在製造陰極160期間可減少對下伏有機層之損害。較佳地，保護層對於其所傳輸之載流子類型(在裝置100中為電子)具有高載流子遷移率，使得其不顯著增加裝置100之運作電壓。CuPc、BCP及各種金屬酞菁為可用於保護層中之材料的實例。可使用其他材料或材料組合。保護層155之厚度較佳足夠厚，使得極少或無由於有機保護層160沈積後進行之製造方法而對下伏層造成之損害，然而不宜過厚以致顯著增加裝置100之運作電壓。保護層155可經摻雜以增加其電導率。舉例而言，CuPc或BCP保護層160可經Li摻雜。關於保護層之更詳細描述可見於Lu等人之美國專利申請案第09/931,948號，其係以引用的方式全部併入。 The protective layer can be used during subsequent manufacturing methods to protect the underlying layer. For example, a method for fabricating a metal or metal oxide top electrode can damage the organic layer, and the protective layer can Used to reduce or eliminate the damage. In device 100, protective layer 155 may reduce damage to the underlying organic layer during fabrication of cathode 160. Preferably, the protective layer has a high carrier mobility for the type of carrier it transports (electrons in device 100) such that it does not significantly increase the operating voltage of device 100. CuPc, BCP and various metal phthalocyanines are examples of materials that can be used in the protective layer. Other materials or combinations of materials can be used. The thickness of the protective layer 155 is preferably sufficiently thick that there is little or no damage to the underlying layer due to the fabrication process performed after the deposition of the organic protective layer 160, but it is not desirable to be too thick to significantly increase the operating voltage of the device 100. The protective layer 155 can be doped to increase its electrical conductivity. For example, the CuPc or BCP protective layer 160 can be doped with Li. A more detailed description of the protective layer can be found in U.S. Patent Application Serial No. 09/931,948, the entire disclosure of which is incorporated herein by reference.
圖2展示倒置型OLED 200。該裝置包括一基板210、一陰極215、一發射層220、一電洞傳輸層225及一陽極230。可藉由依次沈積所述層來製造裝置200。因為最常見之OLED組態具有一安置於陽極上之陰極，且裝置200具有安置於陽極230下之陰極215，所以裝置200可稱為"倒置型" OLED。類似於彼等關於裝置100描述者之材料可用於裝置200之相應層中。圖2提供可如何自裝置100之結構省略某些層的一種實例。 FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be fabricated by depositing the layers in sequence. Since the most common OLED configuration has a cathode disposed on the anode and the device 200 has a cathode 215 disposed under the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the respective layers of device 200. FIG. 2 provides an example of how certain layers may be omitted from the structure of device 100.
藉由非限制性實例之方式提供圖1及2中說明之簡單層狀結構，且應瞭解本發明之實施例可結合多種其他結構使用。所述之特定材料及結構實際上為例示性的，且可使用其他材料及結構。可藉由以不同方式組合所述之各種層達成功能型OLED，或基於設計、效能及成本因素可完全省略各層。亦可包括未具體描述之其他層。可使用除彼等具體描述者以外之材料。儘管本文中提供之許多實例將各種層描述為包含單一材料，但應瞭解可使用諸如主體與摻雜劑之混合物的材料組合，或更通常使用混合物。該等層亦可具有各種子層。對於本文中各種層給定之名稱並不意欲嚴格限制。舉例而言，在裝置200中，電洞 傳輸層225傳輸電洞且將電洞注入發射層220中，且其可描述為電洞傳輸層或電洞注入層。在一實施例中，OLED可描述為具有一安置於陰極與陽極之間的"有機層"。該有機層可包含單一層，或可另外包含如(例如)關於圖1及2所述之不同有機材料之多個層。 The simple layered structure illustrated in Figures 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be utilized in connection with a variety of other structures. The particular materials and structures described are exemplary in nature and other materials and structures may be used. The functional OLEDs can be achieved by combining the various layers described in different ways, or the layers can be completely omitted based on design, performance and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. While many of the examples provided herein describe various layers as comprising a single material, it is to be understood that a combination of materials such as a mixture of a host and a dopant, or more generally a mixture, can be used. The layers can also have various sub-layers. The names given for the various layers in this document are not intended to be strictly limited. For example, in device 200, a hole The transport layer 225 transports holes and injects holes into the emissive layer 220, and it may be described as a hole transport layer or a hole injection layer. In an embodiment, an OLED can be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may comprise a single layer or may additionally comprise multiple layers such as, for example, the different organic materials described with respect to Figures 1 and 2.
亦可使用未具體描述之結構及材料，諸如包含諸如揭示於Friend等人之美國專利第5,247,190號中之聚合材料的OLED(PLED)，該專利係以引用的方式全部併入。進一步舉例而言，可使用具有單一有機層之OLED。OLED可(例如)如Forrest等人之美國專利第5,707,745號中所述堆疊，該專利係以引用的方式全部併入。OLED結構可偏離圖1及2中說明之簡單層狀結構。舉例而言，基板可包括傾斜反射表面以改良外部耦合，諸如如Forrest等人之美國專利第6,091,195號中所述之台式結構及/或如Bulovic等人之美國專利第5,834,893號中所述之坑形構造，該等專利係以引用的方式全部併入。 </ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> </ RTI> <RTIgt; By way of further example, an OLED having a single organic layer can be used. OLEDs can be stacked, for example, as described in U.S. Patent No. 5,707,745, the entire disclosure of which is incorporated herein by reference. The OLED structure can deviate from the simple layered structure illustrated in Figures 1 and 2. For example, the substrate can include a slanted reflective surface to improve the external coupling, such as the slab structure described in U.S. Patent No. 6,091,195 to Forrest et al., and/or the pits as described in U.S. Patent No. 5,834,893 to U.S. Pat. The configurations are hereby incorporated by reference in their entirety.
除非另有說明，否則可藉由任何合適方法沈積各種實施例之層中的任一者。對於有機層而言，較佳方法包括諸如美國專利第6,013,982號及第6,087,196號(其係以引用的方式全部併入)所述之熱蒸發、噴墨，諸如Forrest等人之美國專利第6,337,102號(其係以引用的方式全部併入)中所述之有機氣相沈積(OVPD)及諸如美國專利申請案第10/233,470號(其係以引用的方式全部併入)中所述之藉由有機氣相噴印(OVJP)沈積。其他合適沈積方法包括旋塗及其他基於溶液之方法。較佳在氮或惰性氣氛中進行基於溶液之方法。對於其他層而言，較佳方法包括熱蒸發。較佳之圖案化方法包括諸如美國專利第6,294,398號及第6,468,819號(其係以引用的方式全部併入)中所述之經由遮罩沈積、冷焊，及與某些諸如噴墨及OVJP之沈積方法相關聯之圖案化。亦可使用其他方法。待沈積之材料可經改質以使其與特定沈積方法相容。舉例而言，諸如烷基及芳基之分枝或未分枝且較佳含有 至少3個碳之取代基可用於小分子中以增強其經受溶液處理之能力。可使用具有20個或20個以上碳之取代基，且3-20個碳為較佳範圍。因為不對稱材料可具有較低之再結晶傾向，所以具有不對稱結構之材料可比彼等具有對稱結構者具有更佳之溶液可處理性。樹枝狀聚合物取代基可用以增強小分子經受溶液處理之能力。 Any of the various embodiments may be deposited by any suitable method unless otherwise stated. For organic layers, preferred methods include thermal evaporation, ink jets such as those described in U.S. Patent Nos. 6,013,982 and 6,087,196, the entire disclosures of each of which are incorporated herein by reference. By organic vapor deposition (OVPD) as described in the entire disclosure of which is incorporated by reference, in its entirety by reference in its entirety in its entirety in Organic vapor phase printing (OVJP) deposition. Other suitable deposition methods include spin coating and other solution based methods. The solution based method is preferably carried out in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. The preferred method of patterning includes deposition via masking, cold soldering, and deposition with certain such as inkjet and OVJP, as described in U.S. Patent Nos. 6,294,398 and 6,468,819, all incorporated herein by reference. Method associated with patterning. Other methods can also be used. The material to be deposited can be modified to be compatible with a particular deposition process. For example, branched or unbranched, such as alkyl and aryl groups, preferably contain Substituents of at least 3 carbons can be used in small molecules to enhance their ability to undergo solution processing. A substituent having 20 or more carbons may be used, and 3 to 20 carbons are preferred. Because asymmetric materials can have a lower tendency to recrystallize, materials with asymmetric structures can have better solution treatability than those with symmetric structures. Dendrimer substituents can be used to enhance the ability of small molecules to undergo solution processing.
在不悖離本發明之範疇的情況下，本文所揭示之分子可以許多不同方式經取代。舉例而言，可將取代基添加至具有三個雙齒配位子之化合物，使得在添加取代基之後，雙齒配位子中之一或多者鍵聯在一起以形成(例如)四齒或六齒配位子。可形成其他該等鍵聯。咸信歸因於此項技術中通常理解為"螯合效應"之因素，此類型之鍵聯可相對於無鍵聯之類似化合物增加穩定性。 The molecules disclosed herein may be substituted in many different ways without departing from the scope of the invention. For example, a substituent can be added to a compound having three bidentate ligands such that after the substituent is added, one or more of the bidentate ligands are bonded together to form, for example, a tetradentate Or a six-toothed ligand. Other such linkages can be formed. Salty letters are attributed to factors commonly referred to in the art as "chelating effects", and this type of linkage can increase stability relative to similar compounds without linkages.
可將根據本發明之實施例製造的裝置併入多種消費產品中，包括平板顯示器，電腦監控器、電視、廣告牌、內部或外部照明及/或信號轉導用燈、抬頭顯示器、全透明顯示器、可撓性顯示器、雷射印表機、電話、蜂巢式電話、個人數位助理(PDA)、膝上型電腦、數位攝像機、可攜式攝像機、尋視器、微顯示器、媒介、大面積牆壁、劇場或運動場螢幕或標記。各種控制機制可用以控制根據本發明所製造之裝置，包括被動型矩陣及主動型矩陣。許多裝置意欲用於人類舒適之溫度範圍，諸如18℃至30℃，且更佳在室溫下(20-25℃)。 Devices made in accordance with embodiments of the present invention can be incorporated into a variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, interior or exterior lighting and/or signal transduction lamps, heads-up displays, fully transparent displays , flexible displays, laser printers, telephones, cellular phones, personal digital assistants (PDAs), laptops, digital cameras, camcorders, viewers, microdisplays, media, large-area walls , theater or sports field screen or mark. Various control mechanisms can be used to control the devices made in accordance with the present invention, including passive matrix and active matrix. Many devices are intended for use in human comfort temperature ranges, such as 18 ° C to 30 ° C, and more preferably at room temperature (20-25 ° C).
本文中所述之材料及結構可適用於除OLED以外之裝置中。舉例而言，諸如有機太陽電池及有機光偵測器之其他光電子裝置可採用該等材料及結構。更一般而言，諸如有機電晶體之有機裝置可採用該等材料及結構。 The materials and structures described herein are applicable to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can employ such materials and structures. More generally, organic devices such as organic transistors can employ such materials and structures.
在一態樣中，本發明提供一種包含一第一有機層之有機電子裝置，其中該第一有機層包含交聯金屬錯合物。有機電子裝置可為發光裝置、場效應電晶體、光電裝置及其類似物。在有機發光裝置中，第 一有機層可為諸如電洞傳輸層、電洞注入層、電子傳輸層或電子注入層之電荷傳輸層。 In one aspect, the invention provides an organic electronic device comprising a first organic layer, wherein the first organic layer comprises a crosslinked metal complex. The organic electronic device can be a light emitting device, a field effect transistor, an optoelectronic device, and the like. In an organic light-emitting device, An organic layer may be a charge transport layer such as a hole transport layer, a hole injection layer, an electron transport layer, or an electron injection layer.
在某些情況下，有機電子裝置為包含一第一電極及一第二電極之有機發光裝置，其中該第一有機層係安置於第一電極與第二電極之間。在某些情況下，第一電極為陽極且第一有機層與第一電極直接接觸。 In some cases, the organic electronic device is an organic light emitting device including a first electrode and a second electrode, wherein the first organic layer is disposed between the first electrode and the second electrode. In some cases, the first electrode is an anode and the first organic layer is in direct contact with the first electrode.
金屬錯合物具有某些使其可適於用作電荷傳輸材料之特性。舉例而言，在電洞注入層中使用諸如CuPC之金屬錯合物可提供穩定裝置運作。諸如Ir(III)、Co(III)及Fe(II)錯合物之某些金屬錯合物可經可逆氧化，因此使其適合用作電洞注入或電荷傳輸材料。此外，金屬錯合物之交聯可提供各種可適用於裝置製造及/或運作之功能。舉例而言，交聯可使金屬錯合物附著至基板或其他表面以提供高物理穩定性。 Metal complexes have certain properties that make them suitable for use as charge transport materials. For example, the use of a metal complex such as CuPC in the hole injection layer can provide stable device operation. Certain metal complexes such as Ir(III), Co(III), and Fe(II) complexes can be reversibly oxidized, thus making them suitable for use as hole injection or charge transport materials. In addition, cross-linking of the metal complex provides a variety of functions that are suitable for device fabrication and/or operation. For example, crosslinking can attach a metal complex to a substrate or other surface to provide high physical stability.
在某些情況下，第一有機層為非電致發光的。如本文中所用，術語"非電致發光"意謂該層具有小於1cd/m2之發光。 In some cases, the first organic layer is non-electroluminescent. As used herein, the term "non-electroluminescent" means that the layer has a luminescence of less than 1 cd/m 2 .
交聯金屬錯合物可為交聯有機金屬錯合物，諸如有機金屬銥錯合物。在某些情況下，藉由使可交聯銥錯合物交聯來形成交聯金屬錯合物。可交聯銥錯合物包含一組與中心銥原子配位之配位子。該等配位子中之一或多者已於其上連接有一或多個能夠與其他分子聚合以形成分子間共價鍵之可聚合基團。舉例而言，複數個可交聯銥錯合物可經由其可聚合基團彼此交聯。可聚合基團可位於配位子上之任何位置，且在某些情況下可於配位子上形成端基。 The crosslinked metal complex can be a crosslinked organometallic complex such as an organometallic ruthenium complex. In some cases, a crosslinked metal complex is formed by crosslinking a crosslinkable ruthenium complex. A crosslinkable ruthenium complex comprises a group of ligands coordinated to a central ruthenium atom. One or more of the ligands have attached thereto one or more polymerizable groups capable of polymerizing with other molecules to form intermolecular covalent bonds. For example, a plurality of crosslinkable ruthenium complexes can be cross-linked to each other via their polymerizable groups. The polymerizable group can be located at any position on the ligand and, in some cases, can form a terminal group on the ligand.
在某些情況下，由如下所示之式I來表示可交聯銥錯合物：
各L表示與銥配位之配位子，其包括含有離域π電子或用以改良銥錯合物之溶解性(水溶液或有機溶液)、液晶原基特性或電荷傳輸能力之各種雙齒配位子中的任一者。舉例而言，配位子L可為苯基吡啶或乙醯丙酮。 Each L represents a ligand coordinated to ruthenium, which includes various double-dentate formulations containing delocalized π electrons or to improve the solubility (aqueous solution or organic solution), liquid crystal priming characteristics or charge transporting ability of the ruthenium complex. Any of the seats. For example, the ligand L can be phenylpyridine or acetamidine.
各K亦表示配位子，其包含結構R1-A-B-R2、間隔基S及一或多個可聚合基團P。變數"n"具有介於1至3範圍內之整數值。若n=1，則配位子L可彼此相同或不同。若n=2或n=3，則各配位子K可彼此相同或不同。 Each K also represents a ligand comprising a structure R 1 -ABR 2 , a spacer S and one or more polymerizable groups P. The variable "n" has an integer value in the range of 1 to 3. If n=1, the ligands L may be the same or different from each other. If n=2 or n=3, each of the ligands K may be the same or different from each other.
結構A-B表示彼此鍵結之一對芳環。環A及B各自為5或6員環。環A上之原子X表示雜原子，其可為氮或碳。結構A-B經由環A上之氮原子及環B上之sp2混成化碳與銥配位。 Structure AB represents a pair of aromatic rings bonded to each other. Rings A and B are each a 5 or 6 membered ring. The atom X on ring A represents a hetero atom which may be nitrogen or carbon. Structure AB is coordinated to the ruthenium via a nitrogen atom on ring A and sp 2 on ring B.
環A或B各自可視情況經取代基R1及R2取代，其中R1及R2各自表示一或多個位於其個別環之任何位置的獨立選擇取代基。R1或R2可與其個別環鍵聯或稠合。R1及R2取代基可包括烷基、雜烷基、芳基及雜芳基。 Ring A or B, each optionally substituted with a substituent R 1 and R 2 , wherein R 1 and R 2 each represent one or more independently selected substituents at any position of its individual ring. R 1 or R 2 may be bonded or fused to its individual ring. The R 1 and R 2 substituents may include alkyl groups, heteroalkyl groups, aryl groups, and heteroaryl groups.
如本文中所用，術語"烷基"係指烷基部分且涵蓋直鏈及支鏈烷基鏈。較佳烷基部分為含有1至15個碳原子之烷基部分且其包括甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基及其類似基團。另外，烷基部分自身可經一或多個取代基取代。如本文中所用，術語" 雜烷基"係指包括雜原子之烷基部分。 As used herein, the term "alkyl" refers to an alkyl moiety and encompasses both straight and branched alkyl chains. Preferred alkyl moieties are alkyl moieties having from 1 to 15 carbon atoms and include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and the like. Additionally, the alkyl moiety itself may be substituted with one or more substituents. As used herein, the term " "Heteroalkyl" means an alkyl moiety comprising a hetero atom.
如本文中所用，術語"芳基"係指芳基部分且涵蓋含有至少一個芳環之結構，其包括單環基團及多環系統。多環可具有兩個或兩個以上環，其中兩個原子為兩個毗連環共用(該等環經"稠合")，其中至少一個環為芳環。 As used herein, the term "aryl" refers to an aryl moiety and encompasses structures containing at least one aromatic ring, including monocyclic groups and polycyclic systems. Polycyclic rings can have two or more rings in which two atoms are shared by two contiguous rings (the rings are "fused"), at least one of which is an aromatic ring.
如本文中所用，術語"雜芳基"係指雜芳基部分且涵蓋可包括1至4個雜原子之單環雜芳族基團。雜芳基部分之實例包括吡咯、呋喃、噻吩、咪唑、噁唑、噻唑、***、四唑、吡唑、吡啶、吡嗪及嘧啶及其類似物。術語"雜芳基"亦包括具有兩個或兩個以上環之多環雜芳族系統，其中兩個原子為兩個毗連環共用(該等環經"稠合")，其中至少一個環為雜芳基。其他環可為環烷基、環烯基、芳基、雜環及/或雜芳基。 As used herein, the term "heteroaryl" refers to a heteroaryl moiety and encompasses a monocyclic heteroaromatic group which may include from 1 to 4 heteroatoms. Examples of heteroaryl moieties include pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, tetrazole, pyrazole, pyridine, pyrazine, and pyrimidine and the like. The term "heteroaryl" also includes polycyclic heteroaromatic systems having two or more rings in which two atoms are shared by two contiguous rings (the rings are "fused"), at least one of which is Heteroaryl. Other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic and/or heteroaryl.
在某些情況下，環A可為吡啶、嘧啶、喹啉、異喹啉、咪唑、苯幷咪唑或吡嗪。適用於配位子K中之R1-A-B-R2結構之實例包括：
P表示連接至間隔基S之可聚合基團。如本文中所用，"可聚合基團"係指具有足夠反應性以與另一可交聯銥錯合物、與交聯劑或與共聚單體形成至少一個共價鍵之分子的任何原子、官能基或部分。變數"a"表示間隔基上之可聚合基團的數目且其可具有1-5之整數值。在某些情況下，變數"a"具有2或更大之值。在某些情況下，可聚合基團P為間隔基上之端基。 P represents a polymerizable group attached to the spacer S. As used herein, "polymerizable group" refers to any atom that has sufficient reactivity to form a molecule with at least one covalent bond with another crosslinkable ruthenium complex, with a crosslinking agent or with a comonomer, Functional group or moiety. The variable "a" represents the number of polymerizable groups on the spacer and it may have an integer value of 1-5. In some cases, the variable "a" has a value of 2 or greater. In some cases, the polymerizable group P is an end group on the spacer.
此項技術中已知各種可聚合基團，其包括衍生自胺、醯亞胺、醯胺、醇、酯、環氧化物、矽氧烷、含有不飽和碳-碳鍵之部分及應變環狀化合物之彼等可聚合基團。舉例而言，可聚合基團可為乙烯基、丙烯酸酯、環氧化物、環氧丙烷、三氟乙烯、苯幷環丁烯、矽氧烷、順丁烯二醯亞胺、氰酸酯、乙炔基、橋亞甲基四氫化鄰苯二甲醯亞胺(nadimide)、苯基乙炔基、伸聯苯基、鄰苯二甲腈或酸。在某些情況下，可聚合基團可為乙烯基、矽氧烷或酸。 Various polymerizable groups are known in the art which include derivatives derived from amines, quinones, decylamines, alcohols, esters, epoxides, oxiranes, unsaturated carbon-carbon bonds, and strained rings. These polymerizable groups of the compounds. For example, the polymerizable group can be a vinyl group, an acrylate, an epoxide, a propylene oxide, a trifluoroethylene, a benzoquinone cyclobutene, a decane, a maleimide, a cyanate, Ethynyl, benzylidene tetrahydrogenated nadimide, phenylethynyl, phenylene, phthalonitrile or acid. In some cases, the polymerizable group can be a vinyl group, a decane or acid.
S表示藉由鍵聯或環稠合連接至環A或B之一或兩者之間隔基。間隔基可含有一或多個鍵及/或鍵聯單元。在某些情況下，鍵聯單元可為支鏈。適用於間隔基之鍵聯單元包括伸烷基、伸雜烷基、伸芳基、伸雜芳基、硼烷、醚、酯、胺、亞胺、醯胺、醯亞胺、硫醚及膦單元。 S represents a spacer attached to one or both of the rings A or B by bonding or ring condensing. The spacer may contain one or more linkages and/or linkage units. In some cases, the linkage unit can be a branch. The linking unit suitable for the spacer includes an alkyl group, a heteroalkyl group, an aryl group, a heteroaryl group, a borane, an ether, an ester, an amine, an imine, a decylamine, a quinone imine, a thioether, and a phosphine. unit.
在某些情況下，選擇間隔基以促進可聚合基團參與聚合反應之能力；改良銥錯合物或第一有機層之電化學穩定性；及/或改良有機電子裝置之運作壽命。舉例而言，增加間隔基之長度可藉由降低對可聚合基團之位阻影響而促進聚合。間隔基亦可經設計以具有增加之可撓性或以賦予可聚合基團增加之運動範圍或自由度。在某些情況下，間隔基可藉由至少5個鍵之距離使可聚合基團與該對芳環A或B中之一者分開；且在某些情況下此距離可為至少7個鍵。 In some cases, the spacer is selected to promote the ability of the polymerizable group to participate in the polymerization; to improve the electrochemical stability of the ruthenium complex or the first organic layer; and/or to improve the operational life of the organic electronic device. For example, increasing the length of the spacer can promote polymerization by reducing the steric hindrance to the polymerizable group. The spacers can also be designed to have increased flexibility or to impart increased range of motion or freedom to the polymerizable groups. In some cases, the spacer may separate the polymerizable group from one of the pair of aromatic rings A or B by a distance of at least 5 bonds; and in some cases the distance may be at least 7 bonds .
在某些情況下，間隔基含有氮。舉例而言，間隔基可含有胺 基，諸如三苯基胺結構。在不希望受理論約束之情況下，咸信胺基可調節HOMO及LUMO能級以增強可交聯銥錯合物之電化學特性。因此，含有胺基之間隔基可用於調節或增強有機電子裝置之效能。 In some cases, the spacer contains nitrogen. For example, the spacer may contain an amine Base, such as a triphenylamine structure. Without wishing to be bound by theory, the salty amine group can modulate the HOMO and LUMO energy levels to enhance the electrochemical properties of the crosslinkable ruthenium complex. Thus, an amine group-containing spacer can be used to adjust or enhance the performance of an organic electronic device.
在某些情況下，可交聯銥錯合物為單體單元。單體單元之交聯形成聚合物或聚合基質。在其他情況下，可交聯銥錯合物為可交聯聚合分子或其部分。舉例而言，銥錯合物可構成聚合物之主鏈或構成聚合物鏈上之側基。聚合分子之交聯產生含有銥錯合物之較大聚合物或聚合基質。 In some cases, the crosslinkable ruthenium complex is a monomer unit. Crosslinking of the monomer units forms a polymer or polymeric matrix. In other instances, the crosslinkable ruthenium complex is a crosslinkable polymeric molecule or a moiety thereof. For example, the ruthenium complex can form the backbone of the polymer or form pendant groups on the polymer chain. Crosslinking of polymeric molecules produces larger polymers or polymeric matrices containing ruthenium complexes.
在某些情況下，由如下所示之式II表示可交聯銥錯合物：
在式II中，間隔基S包含L1、L2及L3，其各自獨立地表示直接鍵鍵聯或選自由以下各物組成之群的鍵聯單元：任何單原子、伸烷基、伸雜烷基、伸芳基、伸雜芳基、硼烷、醚、酯、胺、亞胺、醯胺、醯亞胺、硫醚及膦。變數"a"、"b"、"c"及"d"各自具有1-5之整數值。當表示直接鍵鍵聯時，L1、L2或L3由連接兩個相鄰單元之鍵組成。舉例而言，L2可表示L1與L3之間的鍵。在另一實例中，L3可表示環B與L2之間的鍵。此外，L1、L2及L3中之一者以上可為直接鍵鍵聯。因此， 一般熟習此項技術者易於顯而易見，L1、L2及L3可以各種方式組合以表示如由式II表示之銥錯合物。 In Formula II, the spacer S comprises L 1 , L 2 and L 3 , each independently representing a direct bonding or a linking unit selected from the group consisting of: any monoatomic, alkylene, extensible Heteroalkyl, aryl, heteroaryl, borane, ether, ester, amine, imine, decylamine, quinone imine, thioether and phosphine. The variables "a", "b", "c", and "d" each have an integer value of 1-5. When a direct bond is indicated, L 1 , L 2 or L 3 consists of a bond connecting two adjacent cells. For example, L 2 may represent a bond between L 1 and L 3 . In another example, L 3 can represent a bond between ring B and L 2 . Further, one or more of L 1 , L 2 and L 3 may be a direct bond. Thus, in general, readily apparent to those skilled in the art, L 1, L 2, and L 3 may be combined in various ways to represent the iridium complex compound as represented by Formula II.
在某些情況下，式II之可交聯銥錯合物為： 。此處，存在兩個L1單元，其各自 為在苯環上之任意位置處經可聚合基團P取代之苯環。L2為與兩個L1單元鍵結之中間分枝單元。 In some cases, the crosslinkable ruthenium complex of formula II is: . Here, there are two L 1 units each of which is a benzene ring substituted with a polymerizable group P at any position on the benzene ring. L 2 is an intermediate branching unit bonded to two L 1 units.
在某些情況下，式II之可交聯銥錯合物為： 。此特定銥錯合物可以各種方式由 式II表示。在一實例中，L2為與各自表示L1之兩個經P取代之苯環鍵結之氮原子。在另一實例中，L1表示經P取代之N-苯基苯胺結構且L2表示L1與L3之間的鍵。 In some cases, the crosslinkable ruthenium complex of formula II is: . This particular oxime complex can be represented by Formula II in a variety of ways. In one example, L 2 is a nitrogen atom bonded to two P-substituted benzene rings each representing L 1 . In another example, L 1 represents a P-substituted N-phenylaniline structure and L 2 represents a bond between L 1 and L 3 .
在某些情況下，式II之可交聯銥錯合物為： 。此特定銥錯合物可以各種方式由 式II表示。在一實例中，L3為充當L1-L2基團之鍵聯劑的苯環。在另一實例中，L1為經P取代之三苯基胺結構且L2與L3之組合表示L1與環B之間的鍵。 In some cases, the crosslinkable ruthenium complex of formula II is: . This particular oxime complex can be represented by Formula II in a variety of ways. In one example, L 3 is a benzene ring that acts as a linking agent for the L 1 -L 2 group. In another example, L 1 is a P-substituted triphenylamine structure and a combination of L 2 and L 3 represents a bond between L 1 and Ring B.
在另一態樣中，本發明提供一種製造有機發光裝置之方法。該方法包含提供一具有一安置於其上之第一電極的基板。第一有機層係藉由使可交聯金屬錯合物經溶液沈積於第一電極上且隨後使該可交聯金屬錯合物交聯而形成。在某些情況下，第一電極為陽極且第一有機層與第一電極直接接觸。 In another aspect, the invention provides a method of making an organic light emitting device. The method includes providing a substrate having a first electrode disposed thereon. The first organic layer is formed by subjecting the crosslinkable metal complex to solution deposition on the first electrode and subsequently crosslinking the crosslinkable metal complex. In some cases, the first electrode is an anode and the first organic layer is in direct contact with the first electrode.
可藉由將電荷傳輸材料暴露至熱及/或包括UV光、γ射線或X射線之光化輻射來進行交聯。可在於熱或輻射下分解以產生起始交聯反應之自由基或離子的引發劑存在下進行交聯。可在製造裝置期間就地進行交聯。 Crosslinking can be carried out by exposing the charge transport material to heat and/or actinic radiation comprising UV light, gamma rays or X-rays. Crosslinking can be carried out in the presence of an initiator which decomposes under heat or radiation to produce a radical or ion which initiates the crosslinking reaction. Crosslinking can be carried out in situ during the manufacture of the device.
由共價交聯基質形成之有機層可藉由諸如旋塗、噴塗、浸塗、噴墨及其類似技術之溶液處理技術而適用於製造有機裝置。在溶液處理中，使有機層沈積於溶劑中。因此，在多層結構中，任何下伏層較佳對沈積於其上之溶劑具有抗性。 The organic layer formed from the covalently crosslinked matrix can be suitably used in the manufacture of organic devices by solution processing techniques such as spin coating, spray coating, dip coating, ink jet, and the like. In the solution treatment, the organic layer is deposited in a solvent. Therefore, in the multilayer structure, any underlying layer is preferably resistant to the solvent deposited thereon.
因此，在某些情況下，第一有機層之交聯可致使有機層對溶劑具有抗性。因此，第一有機層可避免因沈積於其上之溶劑而溶解、形態受影響或降解。第一有機層可對多種用於製造有機裝置之溶劑具有抗性，該等溶劑包括甲苯、二甲苯、苯甲醚及其他經取代之芳族及脂族溶劑。可重複溶液沈積及交聯方法以產生多層結構。 Thus, in some cases, crosslinking of the first organic layer can render the organic layer resistant to solvents. Therefore, the first organic layer can be prevented from being dissolved, morphologically affected or degraded by the solvent deposited thereon. The first organic layer can be resistant to a variety of solvents used in the manufacture of organic devices, including toluene, xylene, anisole, and other substituted aromatic and aliphatic solvents. The solution deposition and crosslinking methods can be repeated to create a multilayer structure.
在某些情況下，該方法進一步包含在第一有機層上形成第二有機層，其中該第二有機層包含有機電致發光材料。在某些情況下，藉由溶液沈積來形成第二有機層。在某些情況下，第一有機層不溶於用於沈積第二有機層之溶劑。 In some cases, the method further includes forming a second organic layer on the first organic layer, wherein the second organic layer comprises an organic electroluminescent material. In some cases, the second organic layer is formed by solution deposition. In some cases, the first organic layer is insoluble in the solvent used to deposit the second organic layer.
在某些情況下，該方法進一步包含在第一有機層上形成第三有 機層，其中該第三有機層包含電洞傳輸材料且經安置於第一有機層與第二有機層之間。在某些情況下，藉由溶液沈積來形成第三有機層。在某些情況下，第一有機層不溶於用於沈積第三有機層之溶劑。在某些情況下，將第三有機層中之電洞傳輸材料交聯。 In some cases, the method further comprises forming a third on the first organic layer The carrier layer, wherein the third organic layer comprises a hole transport material and is disposed between the first organic layer and the second organic layer. In some cases, the third organic layer is formed by solution deposition. In some cases, the first organic layer is insoluble in the solvent used to deposit the third organic layer. In some cases, the hole transport material in the third organic layer is crosslinked.
在某些情況下，由式I表示可交聯金屬錯合物，其中L為與銥配位之配位子；其中A及B各自為5或6員芳環，且其中A-B表示經由環A上之氮原子及環B上之sp2混成化碳原子與銥配位之芳環鍵結對；其中變數"n"具有1-3之整數值；其中X為碳或氮原子；其中P為可聚合基團，而變數"a"具有1-5之整數值；其中S為包括一或多個各自獨立地選自由以下各基組成之群的鍵聯單元之間隔基：伸烷基、伸雜烷基、伸芳基、伸雜芳基、硼烷、醚、酯、胺、亞胺、醯胺、醯亞胺、硫醚及膦；且其中環A及B各自視情況分別經基團R1及R2取代，其中R1及R2各自表示一或多個位於其個別環之任意位置的獨立選擇取代基，其中取代基各自經稠合或未經稠合，且其中取代基各自獨立地選自由以下各基組成之群：烷基、雜烷基、芳基及雜芳基。 In certain instances, a crosslinkable metal complex is represented by Formula I, wherein L is a coordinator coordinated to ruthenium; wherein A and B are each a 5 or 6 membered aromatic ring, and wherein AB represents via ring A The upper nitrogen atom and the sp 2 mixed carbon atom on ring B are bonded to the argon ring of the ruthenium; wherein the variable "n" has an integer value of 1-3; wherein X is a carbon or nitrogen atom; wherein P is a polymeric group, and the variable "a" has an integer value of from 1 to 5; wherein S is a spacer comprising one or more linking units each independently selected from the group consisting of alkyl, extended An alkyl group, an aryl group, a heteroaryl group, a borane, an ether, an ester, an amine, an imine, a decylamine, a quinone imine, a thioether, and a phosphine; and wherein the rings A and B are each via a group R, as the case may be 1 and R 2, wherein R 1 and R 2 each represents one or more independently selected positioned anywhere their respective substituent rings, where the substituents are each fused or not fused, and wherein the substituents are each independently The group is selected from the group consisting of an alkyl group, a heteroalkyl group, an aryl group, and a heteroaryl group.
在另一態樣中，本發明提供式I之可交聯銥錯合物，其中L為與銥配位之配位子；其中A及B各自為5或6員芳環，且其中A-B表示經由環A上之氮原子及環B上之sp2混成化碳原子與銥配位之芳環鍵結對；其中變數"n"具有1-3之數值；其中P為可聚合基團，而變數"a"具有1-5之整數值；其中S為含有胺基之間隔基；且其中環A及B各自視情況分別經基團R1及R2取代，其中R1及R2各 自表示一或多個取代基，其中該或該等取代基各自位於其個別環之任意位置，其中取代基各自相同或不同，其中取代基各自與其個別環稠合或鍵聯，且其中取代基各自獨立地選自由以下各基組成之群：烷基、雜烷基、芳基及雜芳基。 In another aspect, the invention provides a crosslinkable ruthenium complex of formula I, wherein L is a coordinator coordinated to ruthenium; wherein A and B are each a 5 or 6 membered aromatic ring, and wherein AB represents An aromatic ring-bonded pair of a carbon atom coordinated to a ruthenium via a nitrogen atom on ring A and sp 2 on ring B; wherein the variable "n" has a value of 1-3; wherein P is a polymerizable group, and the variable "a" has an integer value of from 1 to 5; wherein S is a spacer group containing an amine group; and wherein each of the rings A and B is substituted by a group R 1 and R 2 , respectively, wherein R 1 and R 2 each represent a Or a plurality of substituents, wherein the or each substituent is located at any position of its individual ring, wherein the substituents are each the same or different, wherein the substituents are each fused or bonded to their individual rings, and wherein the substituents are each independently The group consisting of the following groups is selected: alkyl, heteroalkyl, aryl and heteroaryl.
在某些情況下，間隔基S由以下結構表示： 或，其中Ar1、Ar2及Ar3各自為芳基。 In some cases, the spacer S is represented by the following structure: or Wherein Ar 1 , Ar 2 and Ar 3 are each an aryl group.
在某些情況下，間隔基S由以下結構表示：
在某些情況下，可交聯銥錯合物為如下文識別之化合物1-9中之任一者。在某些情況下，可交聯銥錯合物為如下文識別之化合物10- 18中之任一者。 In some cases, the crosslinkable ruthenium complex is any of compounds 1-9 as identified below. In some cases, the crosslinkable ruthenium complex is a compound 10 as identified below- 18 of any.
在某些情況下，第一有機層可另外包含可因其電特性而經選擇之各種摻雜劑中之任一者。摻雜劑可用來增加層之電導率。舉例而言，摻雜劑可為強電子受體，諸如F4-TCNQ或參(五氟苯基)硼烷；或強電子供體，諸如三烷基胺、三芳基胺或鹼金屬；或強氧化劑，諸如氯化鐵或碘。此外，可選擇摻雜劑系統來調整電洞注入層與陽極(例如ITO)表面之間的相互作用。接近陽極表面之定域高度摻雜區域可促進電荷注入電洞注入層中。 In some cases, the first organic layer may additionally comprise any of a variety of dopants that may be selected for their electrical properties. A dopant can be used to increase the conductivity of the layer. For example, the dopant can be a strong electron acceptor such as F4-TCNQ or quinone (pentafluorophenyl)borane; or a strong electron donor such as a trialkylamine, a triarylamine or an alkali metal; or a strong oxidizing agent , such as ferric chloride or iodine. Additionally, a dopant system can be selected to adjust the interaction between the hole injection layer and the surface of the anode (eg, ITO). A highly localized highly doped region near the surface of the anode can facilitate charge injection into the hole injection layer.
在某些情況下，摻雜劑可為歐洲專利申請案EP 1,725,079(Iida等人)中所揭示之離子化合物中之任一者。在某些情況下，摻雜劑可為JP2005-075948(Iida等人)中所揭示之電子受體化合物中之任一者。合適摻雜劑之某些實例包括以下： 三苯甲基-肆(五氟苯基)硼酸鹽 In some cases, the dopant can be any of the ionic compounds disclosed in European Patent Application EP 1,725,079 (Iida et al.). In some cases, the dopant may be any one of the electron acceptor compounds disclosed in JP2005-075948 (Iida et al.). Some examples of suitable dopants include the following: Trityl-indole (pentafluorophenyl)borate
CD1 CD1
4-異丙基-4'-甲基-二苯基錪(五氟苯基)硼酸鹽 4-isopropyl-4'-methyl-diphenylphosphonium (pentafluorophenyl)borate
CD2 CD2
N,N-二甲基苯銨-肆(五氟苯基)硼酸鹽 N,N-dimethylanilinium-indole (pentafluorophenyl)borate
CD3 CD3
摻雜劑可以各種方式包括於有機層中。在某些情況下，摻雜劑為獨立且不同於交聯金屬錯合物(主體材料)之分子物質。在其他情況下，將摻雜劑併入主體材料中。將摻雜劑併入主體材料可藉由以側基形式將摻雜劑鍵結至主體材料上，藉由將摻雜劑併入主體材料之主鏈中以便形成共聚物，或藉由在摻雜劑與主體材料之間形成電荷轉移錯合物來實現。 The dopant can be included in the organic layer in various ways. In some cases, the dopant is a molecular species that is independent and different from the crosslinked metal complex (host material). In other cases, the dopant is incorporated into the host material. Incorporating the dopant into the host material may be performed by bonding the dopant to the host material in the form of pendant groups, by incorporating the dopant into the backbone of the host material to form the copolymer, or by doping This is achieved by forming a charge transfer complex between the dopant and the host material.
現將描述本發明之特定代表性實施例，包括如何進行該等實施例。應瞭解，特定方法、材料、條件、製程參數、設備及其類似物不必限制本發明之範疇。 Specific representative embodiments of the invention will now be described, including how to carry out such embodiments. It should be understood that the particular methods, materials, conditions, process parameters, devices, and the like are not necessarily limited to the scope of the invention.
化合物1之合成Synthesis of Compound 1
中間物A：面-雙[2-(2-吡啶基-κN)苯基-κC]-[2-(2-吡啶基-κN)-(5-溴苯基)-κC]銥(III) Intermediate A: Face-bis[2-(2-pyridyl-κN)phenyl-κC]-[2-(2-pyridyl-κN)-(5-bromophenyl)-κC]铱(III)
在排除光之情況下，將2.53g(14.2mmol)N-溴代丁二醯亞胺於200ml二氯甲烷中之溶液逐滴添加至9.3g(14.2mmol)面-參[2-(2-吡啶 基-κN)苯基-κC]銥(III)於2300ml二氯甲烷中之有效攪拌溶液中。將溶液在室溫下進一步攪拌15小時。在減壓下濃縮至200ml之體積後，將溶液與1000ml乙醇混合。隨後，濾出微晶沈澱物，以100ml乙醇洗滌3次且接著在減壓下乾燥。獲得9.3g產物(中間物A)。產物含有約80%之所需單溴產物，10%之起始物質，10%之二溴產物。 In the absence of light, a solution of 2.53 g (14.2 mmol) of N-bromosuccinimide in 200 ml of dichloromethane was added dropwise to 9.3 g (14.2 mmol) of ginseng-[2-(2- Pyridine The base-κN)phenyl-κC] ruthenium (III) is effectively stirred in 2300 ml of dichloromethane. The solution was further stirred at room temperature for 15 hours. After concentrating to a volume of 200 ml under reduced pressure, the solution was mixed with 1000 ml of ethanol. Subsequently, the crystallite precipitate was filtered off, washed 3 times with 100 ml of ethanol and then dried under reduced pressure. 9.3 g of product (Intermediate A) were obtained. The product contained about 80% of the desired monobrominated product, 10% of the starting material, and 10% of the dibrominated product.
中間物B：將2.0g(2.7mmol)面-雙[2-(2-吡啶基-κN)苯基-κC]-[2-(2-吡啶基-κN)-(5-溴苯基)-κC]銥(III)(中間物A)、0.9g(4.1mmol)4-(4,4,5,5-四甲基-1,3,2-二氧雜硼-2-基)苯胺、1.0g(7mmol)碳酸鉀、500mg甲苯、100ml乙醇與50ml水混合且以氮淨化10分鐘。接著向混合物中添加0.3g Pd(PPh3)4。將混合物加熱至回流，歷時30小時。將混合物冷卻至室溫且分離有機層。在減壓下蒸發溶劑且在管柱中使用二氯甲烷作為溶離劑純化殘餘物。獲得1.2g產物(中間物B)。 Intermediate B: 2.0 g (2.7 mmol) of face-bis[2-(2-pyridyl-κN)phenyl-κC]-[2-(2-pyridyl-κN)-(5-bromophenyl) -κC]铱(III) (Intermediate A), 0.9 g (4.1 mmol) of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaboron Benzylamine, 1.0 g (7 mmol) potassium carbonate, 500 mg toluene, 100 ml ethanol were mixed with 50 ml of water and purged with nitrogen for 10 minutes. Next, 0.3 g of Pd(PPh 3 ) 4 was added to the mixture. The mixture was heated to reflux for 30 hours. The mixture was cooled to room temperature and the organic layer was separated. The solvent was evaporated under reduced pressure and the residue was purified using methylene chloride as solvent. 1.2 g of product (Intermediate B) was obtained.
化合物1：在氮下將1.34mmol面-雙[2-(2-吡啶基-κN)苯基-κC]-[2-(2-吡啶基-κN)-(5-(4-胺基苯基)苯基)-κC]銥(III)(中間物B)、0.49g(2.68mmol)4-溴苯乙烯、9mg乙酸鈀、0.08ml於甲苯中之1M三-第三丁基膦及0.39g(4.0mmol)第三丁醇鈉及100ml對二甲苯加熱至110℃，歷時6小時。冷卻至室溫後，將反應混合物傾入500ml甲醇中。收集沈澱物且在管柱中使用甲苯作為溶離劑純化。在純化後獲得0.36g產物(化合物1)。 Compound 1: 1.34 mmol of face-bis[2-(2-pyridyl-κN)phenyl-κC]-[2-(2-pyridyl-κN)-(5-(4-aminobenzene) under nitrogen Base) phenyl)-κC] ruthenium (III) (intermediate B), 0.49 g (2.68 mmol) of 4-bromostyrene, 9 mg of palladium acetate, 0.08 ml of 1 M tri-tert-butylphosphine in toluene and 0.39 g (4.0 mmol) sodium tributoxide and 100 ml p-xylene were heated to 110 ° C for 6 hours. After cooling to room temperature, the reaction mixture was poured into 500 ml of methanol. The precipitate was collected and purified using toluene as a dissolving agent in the column. After purification, 0.36 g of product (Compound 1) was obtained.
化合物2之合成Synthesis of Compound 2
將1.2g(1.47mmol)面-[2-(2-吡啶基-κN)苯基-κC]-雙[2-(2-吡啶基-κN)-(5-溴苯基)-κC]銥(III)、0.6g(4mmol)4-乙烯基苯基酸、0.08g Pd(PPh3)4、0.5g(3.68mmol)碳酸鉀、180ml甲苯、80ml乙醇及60ml水添加至三頸燒瓶中。將混合物以氮淨化20min且接著加熱至回流，歷時20小時。冷卻至室溫後，分離有機相且經硫酸鎂乾燥。在減壓下蒸發溶劑且在管柱中使用1：1之己烷與二氯甲烷作為溶離劑純化殘餘物。分離1.0g產物(化合物2)。 1.2 g (1.47 mmol) of face-[2-(2-pyridyl-κN)phenyl-κC]-bis[2-(2-pyridyl-κN)-(5-bromophenyl)-κC]铱(III), 0.6 g (4 mmol) of 4-vinylphenyl Acid, 0.08 g of Pd(PPh 3 ) 4 , 0.5 g (3.68 mmol) of potassium carbonate, 180 ml of toluene, 80 ml of ethanol and 60 ml of water were added to a three-necked flask. The mixture was purged with nitrogen for 20 min and then heated to reflux for 20 hours. After cooling to room temperature, the organic phase was separated and dried over magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was purified using 1:1 hexane and dichloromethane as solvent. 1.0 g of product (Compound 2) was isolated.
化合物3之合成Synthesis of Compound 3
在氮下將0.02g(0.08mmol)乙酸鈀及0.16ml於甲苯中之1M三-第三丁基膦添加至100ml甲苯中。在氮下攪拌混合物直至顏色消失。接著向該溶液中添加2.0g(2.5mmol)面-[2-(2-吡啶基-κN)苯基-κC]-雙[2-(2-吡啶基-κN)-(5-溴苯基)-κC]銥(III)、1.4g(10mmol)1-萘-1-胺及0.72 g(7.5mmol)第三丁醇鈉。將混合物加熱至回流，歷時20小時。冷卻至室溫後，自甲醇沈澱反應混合物。藉由過濾收集固體且接著在管柱中使用2：1之二氯甲烷與己烷作為溶離劑純化。分離0.6g產物(中間物C)。使0.5g分離產物(中間物C)與2當量4-溴苯乙烯在相同偶合條件下進一步反應以得到0.2g化合物3。 0.02 g (0.08 mmol) of palladium acetate and 0.16 ml of 1 M tri-tert-butylphosphine in toluene were added to 100 ml of toluene under nitrogen. The mixture was stirred under nitrogen until the color disappeared. Next, 2.0 g (2.5 mmol) of face-[2-(2-pyridyl-κN)phenyl-κC]-bis[2-(2-pyridyl-κN)-(5-bromophenyl) was added to the solution. )-κC]铱(III), 1.4g (10mmol) 1-naphthalen-1-amine and 0.72 g (7.5 mmol) sodium tributoxide. The mixture was heated to reflux for 20 hours. After cooling to room temperature, the reaction mixture was precipitated from methanol. The solid was collected by filtration and then purified in a column using 2:1 dichloromethane and hexanes as solvent. 0.6 g of product (Intermediate C) was isolated. 0.5 g of the isolated product (Intermediate C) was further reacted with 2 equivalents of 4-bromostyrene under the same coupling conditions to give 0.2 g of Compound 3.
化合物4之合成Synthesis of Compound 4
在氮下將2mg乙酸鈀及0.02ml於甲苯中之1M三-第三丁基膦添加至40ml二甲苯中。在氮下攪拌混合物直至顏色消失。接著向該溶液中添加1.03g(1.1mmol)含有銥之二胺化合物、0.321g(0.7mmol)4-溴-N-(4-溴苯基)-N-(4-第二丁基苯基)苯胺、0.128g(0.3mmol)3,6-二溴-9-(4-乙烯基苯基)-9H-咔唑及0.58g(6.0mmol)第三丁醇鈉。將混合物加熱至120℃，歷時3小時。添加0.2g碘代苯。使反應進一步反應2小時。冷卻至室溫後，將反應混合物傾入甲醇中。藉由過濾收集沈澱物。接著使用甲苯作為溶劑使固體穿過經三乙胺處理之矽膠管柱。將溶液再次傾入甲醇中。在真空下乾燥後收集0.2g聚合物4。 2 mg of palladium acetate and 0.02 ml of 1 M tri-tert-butylphosphine in toluene were added to 40 ml of xylene under nitrogen. The mixture was stirred under nitrogen until the color disappeared. Next, 1.03 g (1.1 mmol) of a hydrazine-containing diamine compound and 0.321 g (0.7 mmol) of 4-bromo-N-(4-bromophenyl)-N-(4-second butylphenyl group) were added to the solution. Aniline, 0.128 g (0.3 mmol) of 3,6-dibromo-9-(4-vinylphenyl)-9H-carbazole and 0.58 g (6.0 mmol) of sodium tributoxide. The mixture was heated to 120 ° C for 3 hours. 0.2 g of iodobenzene was added. The reaction was further reacted for 2 hours. After cooling to room temperature, the reaction mixture was poured into methanol. The precipitate was collected by filtration. The solid was then passed through a triethylamine treated cartridge column using toluene as the solvent. The solution was again poured into methanol. After drying under vacuum, 0.2 g of polymer 4 was collected.
化合物5之合成Synthesis of Compound 5
中間物D：在氮下將2.14g(2.9mmol)面-雙[2-(2-吡啶基-κN)苯基-κC]-[2-(2-吡啶基-κN)-(5-溴苯基)-κC]銥(III)、1.8g(4.4mmol)酸酯、0.08g(0.09mmol)Pd2(dba)3、0.143g(0.35mmol)sphos、1.85g(8.7mmol)磷酸鉀、100ml甲苯及10ml水加熱至回流，歷時4小時。冷卻至室溫後，分離各層。以硫酸鎂乾燥有機層。蒸發溶劑且藉由管柱使用於己烷中之60%二氯甲烷純化殘餘物。分離2.33g純產物(中間物D)。以LC-MS證實質量。 Intermediate D: 2.14 g (2.9 mmol) of face-bis[2-(2-pyridyl-κN)phenyl-κC]-[2-(2-pyridyl-κN)-(5-bromo) under nitrogen Phenyl)-κC] ruthenium (III), 1.8 g (4.4 mmol) The acid ester, 0.08 g (0.09 mmol) of Pd2(dba) 3 , 0.143 g (0.35 mmol) of sphos, 1.85 g (8.7 mmol) of potassium phosphate, 100 ml of toluene and 10 ml of water were heated to reflux for 4 hours. After cooling to room temperature, the layers were separated. The organic layer was dried over magnesium sulfate. The solvent was evaporated and the residue was purified using EtOAc EtOAc EtOAc 2.33 g of the pure product (Intermediate D) was isolated. The quality was confirmed by LC-MS.
化合物5：將0.48g(0.5mmol)中間物D溶解於40ml無水THF中。向該溶液中添加0.4g甲基三苯基膦溴化物。接著以冰水浴冷卻懸浮液。將1.5ml於THF中之1M第三丁醇鉀逐滴添加至混合物中。使反應混合物升溫至室溫，歷時30分鐘。將反應混合物傾入冰水中且以二氯甲烷萃取。以硫酸鎂乾燥且溶劑蒸發後，藉由管柱使用1：1之己烷與二氯甲烷作為溶劑純化產物(化合物5)。獲得68mg純化合物5。 Compound 5: 0.48 g (0.5 mmol) of Intermediate D was dissolved in 40 mL of dry THF. To this solution was added 0.4 g of methyltriphenylphosphine bromide. The suspension was then cooled in an ice water bath. 1.5 ml of 1 M potassium butoxide in THF was added dropwise to the mixture. The reaction mixture was allowed to warm to rt for 30 min. The reaction mixture was poured into ice water and extracted with dichloromethane. After drying over magnesium sulfate and evaporation of the solvent, the product (compound 5) was purified by using 1:1 hexanes and dichloromethane as solvent. 68 mg of pure compound 5 were obtained.
化合物6之合成Synthesis of Compound 6
中間物E：在4：1之甲苯/水中混合1.99g(2.55mmol)Irppy單酸酯、0.65g(3.06mmol)5-溴間苯二甲醛、0.628g S-Phos、1.62g磷酸鉀。將系統以氮淨化1小時且接著添加0.38g Pd2(dba)3。將混合物加熱至回流隔夜。冷卻至室溫後，以二氯甲烷萃取混合物且以水洗滌。藉由管柱層析使用二氯甲烷作為溶劑純化殘餘物。獲得1.39g中間物E。 Intermediate E: 1.99 g (2.55 mmol) of Irppy single in 4:1 toluene/water Acid ester, 0.65 g (3.06 mmol) of 5-bromoisophthalaldehyde, 0.628 g of S-Phos, and 1.62 g of potassium phosphate. The system was purged with nitrogen for 1 hour and then 0.38 g of Pd 2 (dba) 3 was added . The mixture was heated to reflux overnight. After cooling to room temperature, the mixture was extracted with dichloromethane and washed with water. The residue was purified by column chromatography using dichloromethane as solvent. 1.39 g of intermediate E was obtained.
化合物6：將0.8g中間物E溶解於40mL無水DMSO中。向溶液中添加1.09g CH3PPh3Br。接著將3.05mL於THF中之第三丁醇鹽逐滴添加至混合物中且在室溫下將混合物攪拌2小時。將反應混合物傾入500mL水中且以二氯甲烷萃取。蒸發溶劑後，藉由管柱層析使用50%-75%之二氯甲烷/己烷作為溶劑純化殘餘物。獲得0.35g淺黃色產物(化合物6)。 Compound 6: 0.8 g of Intermediate E was dissolved in 40 mL of anhydrous DMSO. To the solution was added 1.09 g of CH 3 PPh 3 Br. Next, 3.05 mL of the third butoxide salt in THF was added dropwise to the mixture and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into 500 mL of water and extracted with dichloromethane. After evaporating the solvent, the residue was purified by column chromatography using 50%-75% dichloromethane/hexanes as solvent. 0.35 g of a pale yellow product (Compound 6) was obtained.
化合物7之合成Synthesis of Compound 7
中間物F：在4:1之甲苯及水中混合1.0當量Irppy單酸酯、1.2當量1-烯丙基-4-溴苯、0.08當量S-phos及3當量磷酸鉀。將混合物以氮淨化30分鐘。接著在氮下向混合物中添加0.02當量Pd2(dba)3。將混合物加熱至回流隔夜且隨後處理。可藉由管柱層析使用己烷及二氯甲烷之混合物作為溶劑純化偶合產物。 Intermediate F: Mix 1.0 equivalent of Irppy single in 4:1 toluene and water The acid ester, 1.2 equivalents of 1-allyl-4-bromobenzene, 0.08 equivalents of S-phos and 3 equivalents of potassium phosphate. The mixture was purged with nitrogen for 30 minutes. Then 0.02 equivalents of Pd 2 (dba) 3 were added to the mixture under nitrogen. The mixture was heated to reflux overnight and then worked up. The coupled product can be purified by column chromatography using a mixture of hexane and dichloromethane as a solvent.
化合物7：在氮下在無水二氯甲烷中混合1.0當量中間物F、3.0當量三甲氧基矽氧烷與5%當量PtO2。將混合物加熱至回流隔夜。濾出催化劑且可自甲醇沈澱最終產物(化合物7)。 Compound 7: 1.0 equivalent of intermediate F, 3.0 equivalents of trimethoxymethoxyoxane and 5% equivalent of PtO 2 were mixed in anhydrous dichloromethane under nitrogen. The mixture was heated to reflux overnight. The catalyst was filtered off and the final product (compound 7) was precipitated from methanol.
化合物8之合成Synthesis of Compound 8
中間物G：在氮下在無水二甲苯中混合1.0當量中間物B、2.2當量1-烯丙基-4-溴苯、3當量第三丁醇鈉、3%當量乙酸鈀及6%當量tBu3P。接著將混合物加熱至回流，歷時6小時。可經由管柱層析使用己烷與二氯甲烷之混合物作為溶劑分離產物(中間物G)。 Intermediate G: 1.0 equivalent of intermediate B, 2.2 equivalents of 1-allyl-4-bromobenzene, 3 equivalents of sodium tributoxide, 3% equivalent of palladium acetate and 6% equivalent of tBu in anhydrous xylene under nitrogen 3 P. The mixture was then heated to reflux for 6 hours. The product (intermediate G) can be isolated by column chromatography using a mixture of hexane and dichloromethane as a solvent.
化合物8：在氮下在無水二氯甲烷中混合1.0當量中間物F、6.0當量矽氧烷及10%當量PtO2。將混合物加熱至回流隔夜。濾出催化劑且可藉由自甲醇沈澱獲得最終產物(化合物8)。 Compound 8: 1.0 equivalent of intermediate F, 6.0 equivalents of decane and 10% equivalent of PtO 2 were mixed in anhydrous dichloromethane under nitrogen. The mixture was heated to reflux overnight. The catalyst was filtered off and the final product (Compound 8) was obtained by precipitation from methanol.
化合物9之合成Synthesis of Compound 9
中間物H：將1.2g二溴-Irppy、0.86g 3-(三甲基矽烷基)苯基酸、0.07g S-Phos及2.04g磷酸鉀與250mL甲苯及50mL水混合。將系統以氮淨化30分鐘且添加0.04g Pd2(dba)3。將混合物加熱至回流隔夜。冷卻至室溫後，分離有機層。藉由管柱層析使用2：3之二氯甲烷/己烷作為溶劑純化產物，得到0.9g所需產物(中間物H)。 Intermediate H: 1.2 g of dibromo-Irppy, 0.86 g of 3-(trimethyldecyl)phenyl Acid, 0.07 g of S-Phos and 2.04 g of potassium phosphate were mixed with 250 mL of toluene and 50 mL of water. The system was purged with nitrogen for 30 minutes and 0.04 g of Pd 2 (dba) 3 was added . The mixture was heated to reflux overnight. After cooling to room temperature, the organic layer was separated. The product was purified by column chromatography using 2:3 dichloromethane/hexanes as solvent to afford the desired product ( Intermediate H).
化合物9：將0.87g中間物H溶解於50mL無水二氯甲烷中且冷卻至-78℃。向該溶液中添加0.35mL BBr3。使反應混合物緩慢升溫至室溫隔夜。藉由甲醇中止反應且接著添加水。以乙酸乙酯萃取溶液且以水洗滌。接著自己烷沈澱產物。藉由過濾收集沈澱物。將固體再次溶解於乙酸乙酯中且自己烷沈澱，得到0.2g產物(化合物9)。 Compound 9: 0.87 g of Intermediate H was dissolved in 50 mL of dry dichloromethane and cooled to -78. To this solution was added 0.35 mL of BBr 3 . The reaction mixture was allowed to slowly warm to room temperature overnight. The reaction was stopped by methanol and then water was added. The solution was extracted with ethyl acetate and washed with water. The product is then precipitated by own alkane. The precipitate was collected by filtration. The solid was redissolved in ethyl acetate and the residue was precipitated to give 0.2 g (yield 9).
化合物10之合成 Synthesis of Compound 10
中間物I：將8.5g苄基溴及10mL 2-乙氧基乙醇稱量至具有100mL無水THF溶劑之圓底燒瓶中。在冰浴中冷卻溶液且緩慢添加4g NaH。使溶液升溫至室溫且攪拌隔夜。添加乙酸乙酯以中止殘餘NaH。以水洗滌溶液，以MgSO4乾燥且過濾。藉由旋轉蒸發移除溶 劑。將中間物乾燥裝填於矽藻土上且藉由管柱層析使用己烷/乙酸乙酯作為溶離劑純化。 Intermediate I : 8.5 g of benzyl bromide and 10 mL of 2-ethoxyethanol were weighed into a round bottom flask with 100 mL of anhydrous THF solvent. The solution was cooled in an ice bath and 4 g of NaH was slowly added. The solution was allowed to warm to room temperature and stirred overnight. Ethyl acetate was added to stop the residual NaH. Solution was washed with water, dried over MgSO 4 and filtered. The solvent was removed by rotary evaporation. The intermediate was dry-packed on diatomaceous earth and purified by column chromatography using hexane/ethyl acetate as a solvent.
中間物J：將1當量參-5-溴苯基吡啶銥、5當量雙(頻哪醇根基)二硼、0.09當量Pd(dppf)2Cl2及9當量乙酸鉀稱量至以二噁烷用作溶劑之燒瓶中。將溶液以氮淨化且加熱至90℃，歷時12小時。藉由旋轉蒸發移除二噁烷，將固體溶解於二氯甲烷中且以水洗滌。藉由旋轉蒸發移除二氯甲烷且將物質乾燥裝填於矽藻土上且藉由管柱層析使用己烷/二氯甲烷作為溶離劑純化。 Intermediate J : 1 equivalent of cis-5-bromophenylpyridinium, 5 equivalents of bis(pinacolyl)diboron, 0.09 equivalents of Pd(dppf) 2 Cl 2 and 9 equivalents of potassium acetate were weighed to dioxane Used as a solvent in a flask. The solution was purged with nitrogen and heated to 90 ° C for 12 hours. The dioxane was removed by rotary evaporation and the solid was dissolved in dichloromethane and washed with water. Dichloromethane was removed by rotary evaporation and the material was dried and applied to celite and purified by column chromatography using hexane/dichloromethane as solvent.
中間物K：將0.5g(0.48mmol)參-(5-頻哪醇根基硼-苯基吡啶)銥(中間物J)、0.16g(0.63mmol)4-溴苄基醚(中間物I)、0.23g(1.25mmol)4-溴苯甲醛、0.066g(0.072mmol)參(二亞苄基丙酮)二鈀(0)[Pd2(dba)3]、0.12g(0.29mmol)2-二環己基膦基-2',6'-二甲氧基聯苯(SPhos)及0.92g(4.32mmol)磷酸三鉀(K3PO4)稱量至燒瓶中。使用80mL甲苯及20mL水作為溶劑且將溶液以氮淨化。將溶液加熱至回流，歷時12小時。冷卻後，分離有機層且以MgSO4乾燥。藉由管柱層析使用二氯甲烷/乙酸乙酯作為溶離劑(1%乙酸乙酯梯度至50%)分離產物。 Intermediate K : 0.5 g (0.48 mmol) of cis-(5-pinacol-boron boron-phenylpyridine) hydrazine (Intermediate J), 0.16 g (0.63 mmol) of 4-bromobenzyl ether (Intermediate I) 0.23 g (1.25 mmol) 4-bromobenzaldehyde, 0.066 g (0.072 mmol) gin (dibenzylideneacetone) dipalladium (0) [Pd 2 (dba) 3 ], 0.12 g (0.29 mmol) 2- cyclohexyl phosphino-2 ', 6'-dimethoxybiphenyl (SPhos) and 0.92g (4.32mmol) of tripotassium phosphate (K 3 PO 4) was weighed into the flask. 80 mL of toluene and 20 mL of water were used as a solvent and the solution was purged with nitrogen. The solution was heated to reflux for 12 hours. After cooling, the organic layer was separated and dried in MgSO 4. The product was isolated by column chromatography using dichloromethane / ethyl acetate as a solvent (1% ethyl acetate gradient to 50%).
藉由旋轉蒸發移除溶劑且在真空下將產物乾燥隔夜。 The solvent was removed by rotary evaporation and the product was dried under vacuum overnight.
化合物10：在氮下將0.3g(0.28mmol)中間物K及0.51g(1.4mmol)甲基三苯基溴化鏻添加於具有15mL無水DMSO之燒瓶中。藉由注射器緩慢添加1莫耳濃度THF溶液形式之1.4mL(1.4mmol)第三丁醇鉀。在室溫下將溶液攪拌12小時且添加水以使產物沈澱。藉由過濾收集固體，將其溶解於二氯甲烷中且以MgSO4乾燥。藉由旋轉蒸發移除溶劑。將產物乾燥裝填於矽藻土上且藉由管柱層析使用己烷/乙酸乙酯(1：1)作為溶離劑純化。 Compound 10 : 0.3 g (0.28 mmol) of Intermediate K and 0.51 g (1.4 mmol) of methyltriphenylphosphonium bromide were added to a flask having 15 mL of anhydrous DMSO under nitrogen. 1.4 mL (1.4 mmol) of potassium t-butoxide in the form of a 1 molar solution of THF was slowly added by syringe. The solution was stirred at room temperature for 12 hours and water was added to precipitate the product. The solid was collected by filtration, dissolved in dichloromethane and dried at 4 MgSO. The solvent was removed by rotary evaporation. The product was dry-packed on diatomaceous earth and purified by column chromatography using hexane/ethyl acetate (1:1) as solvent.
化合物11之合成 Synthesis of Compound 11
中間物L：將0.5g(0.48mmol)參-(5-頻哪醇根基硼-苯基吡啶)銥(中間物J)、0.46g(2.5mmol)4-溴苯甲醛、0.066g(0.072mmol)參(二亞苄基丙酮)二鈀(0)[Pd2(dba)3]、0.12g(0.29mmol)2-二環己基膦基-2',6'-二甲氧基聯苯(SPhos)及0.92g(4.32mmol)磷酸三鉀(K3PO4)稱量至燒瓶中。使用80mL甲苯及20mL水作為溶劑且將溶液以氮淨化。將溶液加熱至回流，歷時12小時。冷卻後，分離有機層且以MgSO4乾燥。藉由管柱層析使用二氯甲烷/乙酸乙酯作為溶離劑(1%乙酸乙酯)分離產物。藉由旋轉蒸發移除溶劑且在真空下將產物乾燥隔夜。 Intermediate L : 0.5 g (0.48 mmol) of cis-(5-pinacol-boron boron-phenylpyridine) hydrazine ( Intermediate J ), 0.46 g (2.5 mmol) of 4-bromobenzaldehyde, 0.066 g (0.072 mmol)参 (dibenzylideneacetone) dipalladium (0) [Pd 2 (dba) 3 ], 0.12 g (0.29 mmol) 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl ( SPhos) and 0.92 g (4.32 mmol) of tripotassium phosphate (K 3 PO 4 ) were weighed into the flask. 80 mL of toluene and 20 mL of water were used as a solvent and the solution was purged with nitrogen. The solution was heated to reflux for 12 hours. After cooling, the organic layer was separated and dried in MgSO 4. The product was isolated by column chromatography using dichloromethane / ethyl acetate as a solvent (1% ethyl acetate). The solvent was removed by rotary evaporation and the product was dried under vacuum overnight.
化合物11：將0.2g(0.21mmol)中間物L及0.37g(1.03mmol)甲基三苯基溴化鏻添加至具有15mL無水DMSO之燒瓶中。藉由注射器緩慢添加1.03mL之1莫耳濃度溶液形式之第三丁醇鉀。在室溫下將溶液攪拌12小時且添加水以使產物沈澱。藉由過濾收集固體，將其溶解於二氯甲烷中且以MgSO4乾燥。藉由旋轉蒸發移除溶劑。將產物乾燥裝 填於矽藻土上且藉由管柱層析使用己烷/甲苯(1：0至1：4)作為溶離劑純化。 Compound 11 : 0.2 g (0.21 mmol) of intermediate L and 0.37 g (1.03 mmol) of methyltriphenylphosphonium bromide were added to a flask having 15 mL of anhydrous DMSO. Potassium tert-butoxide in the form of 1.03 mL of a 1 molar solution was slowly added by syringe. The solution was stirred at room temperature for 12 hours and water was added to precipitate the product. The solid was collected by filtration, dissolved in dichloromethane and dried at 4 MgSO. The solvent was removed by rotary evaporation. The product was dry-packed on diatomaceous earth and purified by column chromatography using hexane/toluene (1:0 to 1:4) as a solvent.
化合物12之合成 Synthesis of Compound 12
中間物M：將0.6g(0.772mmol)酸酯、0.78g(2.3mmol)醛、0.05g(4mol%)S-Phos、1.1g(4.6mmol)磷酸鉀、100ml甲苯及10ml水添加至三頸燒瓶中。將燒瓶以氮淨化20分鐘，之後添加0.03g Pd2(dba)3。將混合物加熱至回流，歷時14小時。冷卻至室溫後，分離有機層且經硫酸鎂乾燥。蒸發溶劑後，藉由矽膠管柱使用1：4之二氯甲烷/己烷作為溶離劑純化殘餘物。收集0.35g所需產物。 Intermediate M: 0.6g (0.772mmol) The acid ester, 0.78 g (2.3 mmol) of aldehyde, 0.05 g (4 mol%) of S-Phos, 1.1 g (4.6 mmol) of potassium phosphate, 100 ml of toluene and 10 ml of water were added to a three-necked flask. The flask was purged with nitrogen for 20 minutes, after which 0.03 g of Pd 2 (dba) 3 was added . The mixture was heated to reflux for 14 hours. After cooling to room temperature, the organic layer was separated and dried over magnesium sulfate. After evaporating the solvent, the residue was purified by using a silica gel column eluted with 1:4 dichloromethane/hexane as solvent. 0.35 g of the desired product was collected.
化合物12：將0.25g(0.21mmol)中間物M及0.23g(0.64mmol)甲 基三苯基膦溴化物溶解於20ml DMSO中。向該溶液中逐滴添加0.64ml於THF中之1.0M tBuOK。使反應反應隔夜。添加甲醇以使產物沈澱。藉由過濾收集沈澱物。藉由管柱使用3：1之甲苯/己烷純化產物。在純化後收集0.12g純產物。 Compound 12: 0.25 g (0.21 mmol) of intermediate M and 0.23 g (0.64 mmol) of A The triphenylphosphine bromide was dissolved in 20 ml of DMSO. To the solution was added dropwise 0.64 ml of 1.0 M tBuOK in THF. The reaction was allowed to react overnight. Methanol was added to precipitate the product. The precipitate was collected by filtration. The product was purified by column using 3:1 toluene/hexanes. 0.12 g of pure product was collected after purification.
化合物13之合成 Synthesis of Compound 13
中間物N：在三頸燒瓶中將1.2g(32mmol)4,4'-(4-溴苯基氮烷二基)二苯甲醛、1.08g(2.9mmol)酸酯、0.1g(0.23mmol)S-Phos及2.1g(8.7mmol)磷酸鉀與100ml甲苯及10ml水混合。將混合物以氮淨化20分鐘。將0.05g Pd2(dba)3添加至混合物中。將反應加熱至回流隔 夜。冷卻至室溫後，分離有機層且以硫酸鎂乾燥。藉由管柱層析使用於二氯甲烷中之5%乙酸乙酯作為溶離劑純化產物。收集1.3g所需產物(產率：82%)。 Intermediate N: 1.2 g (32 mmol) of 4,4'-(4-bromophenylazanediyl)benzaldehyde, 1.08 g (2.9 mmol) in a three-necked flask The acid ester, 0.1 g (0.23 mmol) of S-Phos and 2.1 g (8.7 mmol) of potassium phosphate were mixed with 100 ml of toluene and 10 ml of water. The mixture was purged with nitrogen for 20 minutes. 0.05 g of Pd 2 (dba) 3 was added to the mixture. The reaction was heated to reflux overnight. After cooling to room temperature, the organic layer was separated and dried over magnesium sulfate. The product was purified by column chromatography using 5% ethyl acetate in dichloromethane as solvent. 1.3 g of the desired product was collected (yield: 82%).
中間物O：將1.25g(2.3mmol)中間物N溶解於50ml二氯甲烷中。添加0.45g(5.75mmol)吡啶。以冰水浴冷卻溶液。向溶液中逐滴添加0.46ml(5.75mmol)三氟甲磺酸酐。在0℃下使溶液反應15min，接著以水中止。以管柱使用2：1之二氯甲烷/己烷作為溶離劑純化後，收集0.56g產物。 Intermediate O: 1.25 g (2.3 mmol) of intermediate N was dissolved in 50 ml of dichloromethane. 0.45 g (5.75 mmol) of pyridine was added. The solution was cooled in an ice water bath. 0.46 ml (5.75 mmol) of trifluoromethanesulfonic anhydride was added dropwise to the solution. The solution was allowed to react at 0 ° C for 15 min, then stopped in water. After purifying the column with 2:1 dichloromethane/hexane as the eluent, 0.56 g of product was collected.
中間物P：以與中間物N相同之方式使0.56g(0.83mmol)中間物O、0.63g(0.69mmol)銥酸酯、0.012g(0.014mmol)Pd2(dba)3、0.023g(0,056mmol)S-Phos、0.48g K3PO4、50ml甲苯及5ml水反應。藉由管柱層析使用二氯甲烷作為溶離劑純化產物。分離0.75g(92%產率)所需產物。 Intermediate P: 0.56 g (0.83 mmol) of intermediate O, 0.63 g (0.69 mmol) of hydrazine in the same manner as the intermediate N The acid ester was reacted with 0.012 g (0.014 mmol) of Pd 2 (dba) 3 , 0.023 g (0,056 mmol) of S-Phos, 0.48 g of K 3 PO 4 , 50 ml of toluene and 5 ml of water. The product was purified by column chromatography using dichloromethane as the eluent. 0.75 g (92% yield) of the desired product was isolated.
化合物13：將0.65g(0.55mmol)中間物P及0.69g(1.92mmol)MePPh3Br溶解於30ml DMSO中。向該溶液中逐滴添加1.65ml之1.0M tBuOK。在室溫下攪拌隔夜後，自100ml甲醇沈澱產物。藉由管柱層析使用2：1之甲苯/己烷純化產物。分離0.26g(40%產率)所需產物。 Compound 13: 0.65 g (0.55 mmol) of intermediate P and 0.69 g (1.92 mmol) of MePPh 3 Br were dissolved in 30 ml of DMSO. To the solution was added 1.65 ml of 1.0 M tBuOK dropwise. After stirring overnight at room temperature, the product was precipitated from 100 mL of methanol. The product was purified by column chromatography using 2:1 toluene/hexanes. 0.26 g (40% yield) of the desired product was isolated.
化合物14之合成 Synthesis of Compound 14
中間物Q：將1g(1.23mmol)雙(5-溴-2-苯基吡啶)-2-苯基吡啶銥、0.75g(4.9mmol)3-甲醯基苯基酸、0.11g(0.123mmol)參(二亞苄基丙酮)二鈀(0)[Pd2(dba)3]、0.2g(0.49mmol)2-二環己基膦基-2',6'-二甲氧基聯苯(SPhos)及1.6g(7.4mmol)磷酸三鉀(K3PO4)稱量至燒瓶中。使用80mL甲苯及20mL水作為溶劑且將溶液以氮淨化。將溶液加熱至回流，歷時12小時。冷卻後，分離有機層且以MgSO4乾燥。藉由管柱層析使用二氯甲烷/乙酸乙酯作為溶離劑(1%乙酸乙酯)分離產物。藉由旋轉蒸發移除溶劑且在真空下將產物乾燥隔夜。 Intermediate Q : 1 g (1.23 mmol) of bis(5-bromo-2-phenylpyridine)-2-phenylpyridinium, 0.75 g (4.9 mmol) of 3-methylnonylphenyl Acid, 0.11 g (0.123 mmol) ginsyl (dibenzylideneacetone) dipalladium (0) [Pd 2 (dba) 3 ], 0.2 g (0.49 mmol) 2-dicyclohexylphosphino-2', 6'- Dimethoxybiphenyl (SPhos) and 1.6 g (7.4 mmol) of tripotassium phosphate (K 3 PO 4 ) were weighed into the flask. 80 mL of toluene and 20 mL of water were used as a solvent and the solution was purged with nitrogen. The solution was heated to reflux for 12 hours. After cooling, the organic layer was separated and dried in MgSO 4. The product was isolated by column chromatography using dichloromethane / ethyl acetate as a solvent (1% ethyl acetate). The solvent was removed by rotary evaporation and the product was dried under vacuum overnight.
化合物14：將0.6g(0.69mmol)中間物Q及1.24g(3.5mmol)甲基三苯基溴化鏻添加至具有35mL無水DMSO之燒瓶中。藉由注射器緩慢添加3.5mL(3.5mmol)之1莫耳濃度溶液形式之第三丁醇鉀。在室溫下將溶液攪拌12小時且添加水以使產物沈澱。藉由過濾收集固體，將其溶解於二氯甲烷中且以MgSO4乾燥。藉由旋轉蒸發移除溶劑。將產 物乾燥裝填於矽藻土上且藉由管柱層析使用己烷/甲苯(1：0至1：4)作為溶離劑純化。 Compound 14 : 0.6 g (0.69 mmol) of intermediate Q and 1.24 g (3.5 mmol) of methyltriphenylphosphonium bromide were added to a flask with 35 mL of anhydrous DMSO. Potassium tert-butoxide in the form of a 3.5 mL (3.5 mmol) 1 molar solution was slowly added by syringe. The solution was stirred at room temperature for 12 hours and water was added to precipitate the product. The solid was collected by filtration, dissolved in dichloromethane and dried at 4 MgSO. The solvent was removed by rotary evaporation. The product was dry-packed on diatomaceous earth and purified by column chromatography using hexane/toluene (1:0 to 1:4) as a solvent.
化合物15之合成 Synthesis of Compound 15
中間物R：以與中間物Q相同之方式，使2.6g酸酯(6.46mmol)、1.75g(2.15mmol)二溴(Irppy)、0.079g(0.086mmol)Pd2(dba)3、0.15g(0.344mmol)S-Phos及3.0g(12.9mmol)K3PO4於300ml甲苯及30ml水中反應。藉由管柱層析使用二氯甲烷作為溶離劑純化產物。分離1.2g(60%產率)所需產物。 Intermediate R: 2.6 g in the same manner as the intermediate Q Acid ester (6.46 mmol), 1.75 g (2.15 mmol) of dibromo (Irppy), 0.079 g (0.086 mmol) of Pd 2 (dba) 3 , 0.15 g (0.344 mmol) of S-Phos and 3.0 g (12.9 mmol) of K 3 PO 4 was reacted in 300 ml of toluene and 30 ml of water. The product was purified by column chromatography using dichloromethane as the eluent. 1.2 g (60% yield) of the desired product was isolated.
化合物15：將1g(0.84mmol)中間物R及1.0g(2.9mmol)甲基三苯 基溴化鏻溶解於40ml DMSO中。向該溶液中逐滴添加2.5ml之1.0M tBuOK。自甲醇沈澱產物。藉由管柱層析使用2：1之甲苯/己烷作為溶離劑純化產物。分離0.75g(75%產率)所需產物。 Compound 15: 1 g (0.84 mmol) of intermediate R and 1.0 g (2.9 mmol) of methyltriphenylphosphonium bromide were dissolved in 40 ml of DMSO. To this solution was added dropwise 2.5 ml of 1.0 M tBuOK. The product was precipitated from methanol. The product was purified by column chromatography using 2:1 toluene/hexane as the solvent. 0.75 g (75% yield) of the desired product was isolated.
化合物16之合成 Synthesis of Compound 16
中間物S：將2g(6.4mmol)3,3'-二溴聯苯、0.96g(6.4mmol)3-甲 醯基苯基酸、0.072g(0.32mmol)乙酸鈀、0.34g(1.28mmol)三苯基膦及2.65g(19.2mmol)碳酸鉀稱量至以80mL甲苯及20mL水作為溶劑之燒瓶中。將溶液以氮淨化。將溶液加熱至回流，歷時12小時。冷卻後，分離有機層且以MgSO4乾燥。藉由管柱層析使用己烷/乙酸乙酯作為溶離劑(5%乙酸乙酯)分離產物。 Intermediate S : 2 g (6.4 mmol) of 3,3'-dibromobiphenyl, 0.96 g (6.4 mmol) of 3-methyldecylphenyl Acid, 0.072 g (0.32 mmol) of palladium acetate, 0.34 g (1.28 mmol) of triphenylphosphine and 2.65 g (19.2 mmol) of potassium carbonate were weighed into a flask containing 80 mL of toluene and 20 mL of water as a solvent. The solution was purged with nitrogen. The solution was heated to reflux for 12 hours. After cooling, the organic layer was separated and dried in MgSO 4. The product was isolated by column chromatography using hexane/ethyl acetate as a solvent (5% ethyl acetate).
中間物T：將2.5g(7.4mmol)3-溴-間-聯三苯甲醛(中間物S)、1.9g(7.4mmol)雙(頻哪醇根基)二硼、0.18g(0.22mmol)Pd(dppf)2Cl2及2.17g(22.2mmol)乙酸鉀稱量至使用無水二噁烷作為溶劑之燒瓶中。將溶液以氮淨化且加熱至80℃，歷時12小時。藉由旋轉蒸發移除二噁烷，將固體溶解於二氯甲烷中且以水洗滌。以MgSO4乾燥溶液，藉由旋轉蒸發移除溶劑且將物質乾燥裝填於矽藻土上且藉由管柱層析使用己烷/乙酸乙酯作為溶離劑純化。 Intermediate T : 2.5 g (7.4 mmol) of 3-bromo-m-terphenylbenzaldehyde ( intermediate S ), 1.9 g (7.4 mmol) of bis(pinacolyl)diboron, 0.18 g (0.22 mmol) of Pd (dppf) 2 Cl 2 and 2.17 g (22.2 mmol) of potassium acetate were weighed into a flask using anhydrous dioxane as a solvent. The solution was purged with nitrogen and heated to 80 ° C for 12 hours. The dioxane was removed by rotary evaporation and the solid was dissolved in dichloromethane and washed with water. In the solution dried over MgSO 4, solvent was removed by rotary evaporation and the material was dried over diatomaceous earth and loaded by column chromatography using hexane / ethyl acetate as solvent was purified from the agent.
中間物U：將1.25g(1.56mmol)雙(5-溴-2-苯基吡啶)-2-苯基吡啶銥、2.4g(6.25mmol)3-頻哪醇根基硼-間-聯三苯甲醛(中間物T)、0.14g(0.156mmol)參(二亞苄基丙酮)二鈀(0)[Pd2(dba)3]、0.25g(0.62mmol)2-二環己基膦基-2',6'-二甲氧基聯苯(SPhos)及2g(9.36mmol)磷酸三鉀(K3PO4)稱量至燒瓶中。使用80mL甲苯及20mL水作為溶劑且將溶液以氮淨化。將溶液加熱至回流，歷時12小時。冷卻後，分離有機層且以MgSO4乾燥。藉由管柱層析使用二氯甲烷/乙酸乙酯作為溶離劑(2%乙酸乙酯)分離產物。藉由旋轉蒸發移除溶劑且在真空下將產物乾燥隔夜。 Intermediate U: 1.25 g (1.56 mmol) of bis(5-bromo-2-phenylpyridine)-2-phenylpyridinium, 2.4 g (6.25 mmol) of 3-pinacol boron-m-triphenyl Formaldehyde ( intermediate T ), 0.14 g (0.156 mmol) of ginseng (dibenzylideneacetone) dipalladium (0) [Pd 2 (dba) 3 ], 0.25 g (0.62 mmol) of 2-dicyclohexylphosphino-2 '6'-Dimethoxybiphenyl (SPhos) and 2 g (9.36 mmol) of tripotassium phosphate (K 3 PO 4 ) were weighed into a flask. 80 mL of toluene and 20 mL of water were used as a solvent and the solution was purged with nitrogen. The solution was heated to reflux for 12 hours. After cooling, the organic layer was separated and dried in MgSO 4. The product was isolated by column chromatography using dichloromethane/ethyl acetate as a solvent (2% ethyl acetate). The solvent was removed by rotary evaporation and the product was dried under vacuum overnight.
化合物16：將1.3g(1.11mmol)中間物U及2.0g(5.56mmol)甲基三苯基溴化鏻添加至具有40mL無水DMSO之燒瓶中。藉由注射器緩慢添加5.56mL(5.56mmol)1莫耳濃度溶液形式之第三丁醇鉀。在室溫下將溶液攪拌12小時且添加甲醇以使產物沈澱。藉由過濾收集固體，將其溶解於二氯甲烷中且以MgSO4乾燥。藉由旋轉蒸發移除溶劑。將產 物乾燥裝填於矽藻土上且藉由管柱層析使用己烷/甲苯(1：0至1：4)作為溶離劑純化。 Compound 16 : 1.3 g (1.11 mmol) of intermediate U and 2.0 g (5.56 mmol) of methyltriphenylphosphonium bromide were added to a flask with 40 mL of anhydrous DMSO. Potassium tert-butoxide in the form of a 5.56 mL (5.56 mmol) 1 molar solution was slowly added by syringe. The solution was stirred at room temperature for 12 hours and methanol was added to precipitate the product. The solid was collected by filtration, dissolved in dichloromethane and dried at 4 MgSO. The solvent was removed by rotary evaporation. The product was dry-packed on diatomaceous earth and purified by column chromatography using hexane/toluene (1:0 to 1:4) as a solvent.
化合物17之合成 Synthesis of Compound 17
中間物V：將2.0g(2.24mmol)參-5-溴苯基吡啶銥錯合物、0.65g(2.99mmol)4-(4,4,5,5-四甲基-1,3,2-二氧雜硼-2-基)苯胺、1.56g(5.98mmol)2-(4-異丁基苯基)-4,4,5,5-四甲基-1,3,2-二氧雜硼、0.31g(0.33mmol)參(二亞苄基丙酮)二鈀(0)[Pd2(dba)3]、0.55g(1.34mmol)2-二環己基膦基-2',6'-二甲氧基聯苯(SPhos)及2.4g(11.2mmol)磷酸三鉀(K3PO4)稱量至燒瓶中。使用80mL甲苯及20mL水作為溶劑且將溶液以氮淨化。將溶液加熱至回流，歷時12小時。冷卻後，分離有機層且以MgSO4乾燥。藉由管柱層析使用二氯甲烷分離產物。藉由 旋轉蒸發移除溶劑。 Intermediate V: 2.0 g (2.24 mmol) of cis-5-bromophenylpyridinium complex, 0.65 g (2.99 mmol) of 4-(4,4,5,5-tetramethyl-1,3,2 -dioxaboron Benzylamine, 1.56 g (5.98 mmol) of 2-(4-isobutylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaboron , 0.31 g (0.33 mmol) of ginsyl (dibenzylideneacetone) dipalladium (0) [Pd 2 (dba) 3 ], 0.55 g (1.34 mmol) of 2-dicyclohexylphosphino-2', 6'-di Methoxybiphenyl (SPhos) and 2.4 g (11.2 mmol) of tripotassium phosphate (K 3 PO 4 ) were weighed into the flask. 80 mL of toluene and 20 mL of water were used as a solvent and the solution was purged with nitrogen. The solution was heated to reflux for 12 hours. After cooling, the organic layer was separated and dried in MgSO 4. The product was isolated by column chromatography using dichloromethane. The solvent was removed by rotary evaporation.
化合物17：將0.0043g(0.019mmol)乙酸鈀與38μL(0.038mmol)於甲苯溶液中之1M溶液形式的三-第三丁基膦(tBu)3P合併於2mL甲苯中且攪拌30分鐘。將0.64g(0.63mmol)中間物V、149μL(1.14mmol)4-溴苯乙烯、0.18g(1.9mmol)第三丁醇鈉(NaOtBu)與額外之6mL甲苯一起添加。在氮下使溶液回流4小時。以甲醇使產物沈澱、過濾且以甲醇洗滌。將產物乾燥裝填於矽藻土上且藉由管柱層析使用己烷/甲苯(1：0至1：4)作為溶離劑純化。 Compound 17 : 0.0043 g (0.019 mmol) of palladium acetate and 38 μL (0.038 mmol) of tri-tert-butylphosphine (tBu) 3 P in the form of a 1 M solution in toluene were combined in 2 mL of toluene and stirred for 30 minutes. 0.64 g (0.63 mmol) of intermediate V, 149 μL (1.14 mmol) of 4-bromostyrene, 0.18 g (1.9 mmol) of sodium tributoxide (NaOtBu) were added together with an additional 6 mL of toluene. The solution was refluxed for 4 hours under nitrogen. The product was precipitated with methanol, filtered and washed with methanol. The product was dry-packed on diatomaceous earth and purified by column chromatography using hexane/toluene (1:0 to 1:4) as a solvent.
化合物18之合成：化合物18可經由以下流程合成：
裝置實例Device instance
使用旋塗及真空熱蒸發製造所有實例有機發光裝置，且其具有圖3中所示之架構。在預塗有120nm厚氧化銦錫(ITO)陽極之玻璃基板上製造該等裝置。陰極為0.7nm之LiF層，接著為100nm鋁。製造後立即在氮(<1ppm H2O及O2)下以經環氧樹脂密封之玻璃蓋囊封所有裝置且將吸濕劑併入各裝置內。 All of the example organic light-emitting devices were fabricated using spin coating and vacuum thermal evaporation, and which had the architecture shown in FIG. The devices were fabricated on a glass substrate precoated with a 120 nm thick indium tin oxide (ITO) anode. The cathode was a 0.7 nm LiF layer followed by 100 nm aluminum. Immediately after the production with epoxy resin to seal the cover glass capsule under nitrogen (<1ppm H 2 O and O 2) within the sealing means and the respective means all incorporated moisture absorbent.
對於比較實例1之裝置而言，製造由以下各物組成之有機堆疊：作為電洞注入層(HIL)之PEDOT/PSS；作為電洞傳輸層(HTL)之厚度為30nm之N4,N4'-二(萘-1-基)-N4,N4'-雙(4-乙烯基苯基)聯苯-4,4'-二胺；作為發射層之厚度為30nm之摻雜有參(2-(聯苯-3-基)-4-第三丁基吡啶)銥(III)之3,5-二(9H-咔唑-9-基)聯苯；作為第一電子傳輸層(ETL1)之厚度為10nm之BAlq[鋁(III)雙(2-甲基-8-羥基喹啉根基)4-苯基酚鹽]；及作為第二電子傳輸層(ETL2)之厚度為40nm之Alq3[8-參-羥基喹啉鋁]。 For the apparatus of Comparative Example 1, an organic stack consisting of: PEDOT/PSS as a hole injection layer (HIL); N 4 , N 4 having a thickness of 30 nm as a hole transport layer (HTL) was fabricated. ' -Bis(naphthalen-1-yl)-N 4 ,N 4 '-bis(4-vinylphenyl)biphenyl-4,4'-diamine; doped with a thickness of 30 nm as an emissive layer (2-(biphenyl-3-yl)-4-t-butylpyridine) ruthenium (III) 3,5-bis(9H-carbazol-9-yl)biphenyl; as the first electron transport layer ( ETL1) has a thickness of 10 nm of BAlq [aluminum (III) bis(2-methyl-8-hydroxyquinolinyl) 4-phenylphenolate]; and as a second electron transport layer (ETL2), the thickness is 40 nm Alq 3 [8-gin-hydroxyquinoline aluminum].
藉由旋塗沈積PEDOT/PSS層、電洞傳輸層及發射層。對於PEDOT/PSS層而言，歷時30秒鐘將溶液以4000rpm旋塗至ITO上。在200℃下將薄膜烘焙10分鐘且接著放入手套箱中。對於電洞傳輸層而言，歷時30秒鐘將1.0重量%之N4,N4'-二(萘-1-基)-N4,N4'-雙(4-乙烯基苯基)聯苯-4,4'-二胺於甲苯中之溶液以2000rpm旋塗至電洞注入層上。接著在170℃下於手套箱中之加熱板上將薄膜烘焙30分鐘。烘焙後薄膜變成不溶性薄膜。冷卻至室溫後，藉由歷時30秒鐘將1.0重量%主體-1及摻雜劑顏料綠-1(主體與摻雜劑比率為88：12)之溶液以1000rpm旋塗至電洞傳輸層上來沈積發射層。接著將發射層在100℃下烘焙1小時。藉由真空熱蒸發沈積其他層。 The PEDOT/PSS layer, the hole transport layer, and the emission layer are deposited by spin coating. For the PEDOT/PSS layer, the solution was spin coated onto the ITO at 4000 rpm for 30 seconds. The film was baked at 200 ° C for 10 minutes and then placed in a glove box. For the hole transport layer, 1.0% by weight of N 4 , N 4 '-bis(naphthalen-1-yl)-N 4 , N 4 '-bis(4-vinylphenyl) is bonded for 30 seconds. A solution of benzene-4,4'-diamine in toluene was spin-coated onto the hole injection layer at 2000 rpm. The film was then baked at 170 ° C for 30 minutes on a hot plate in a glove box. The film becomes an insoluble film after baking. After cooling to room temperature, a solution of 1.0 wt% of host-1 and dopant pigment green-1 (host to dopant ratio of 88:12) was spin coated to the hole transport layer at 1000 rpm over a period of 30 seconds. The deposition layer is deposited. The emissive layer was then baked at 100 ° C for 1 hour. The other layers were deposited by vacuum thermal evaporation.
以類似於比較實例1之裝置的方式製造實例1之裝置。歷時30秒鐘自化合物1於環己酮中之0.5重量%溶液以4000rpm旋塗電洞注入層。對於電洞傳輸層而言，歷時30秒鐘將1.0重量%之N4,N4'-二(萘-1-基)-N4,N4'-雙(4-乙烯基苯基)聯苯-4,4'-二胺於甲苯中之溶液以4000rpm旋塗至電洞注入層上。接著在200℃下於手套箱中之加熱板上將薄膜烘焙30分鐘。烘焙後薄膜變成不溶性薄膜。冷卻至室溫後，藉由歷時30秒鐘將0.75重量%主體-1及摻雜劑顏料綠-1(主體與摻雜劑比率為88：12)之溶液以1000rpm旋塗至電洞傳輸層上來沈積發射層。接著將 發射層在100℃下烘焙1小時。藉由真空熱蒸發沈積其他層。 The apparatus of Example 1 was fabricated in a manner similar to that of Comparative Example 1. The hole injection layer was spin-coated at 4000 rpm from a 0.5 wt% solution of Compound 1 in cyclohexanone over 30 seconds. For the hole transport layer, 1.0% by weight of N 4 , N 4 '-bis(naphthalen-1-yl)-N 4 , N 4 '-bis(4-vinylphenyl) is bonded for 30 seconds. A solution of benzene-4,4'-diamine in toluene was spin-coated onto the hole injection layer at 4000 rpm. The film was then baked at 200 ° C for 30 minutes on a hot plate in a glove box. The film becomes an insoluble film after baking. After cooling to room temperature, a solution of 0.75 wt% of host-1 and dopant pigment green-1 (host to dopant ratio of 88:12) was spin coated to the hole transport layer at 1000 rpm over a period of 30 seconds. The deposition layer is deposited. The emissive layer was then baked at 100 ° C for 1 hour. The other layers were deposited by vacuum thermal evaporation.
使實例1及比較實例1之裝置在DC電流下運作，產生1000cd/m2之初始亮度。此處裝置壽命定義為在室溫下在恆定DC驅動下，亮度衰減至初始水平之80%逝去的時間。與在電洞注入層中使用化合物1之裝置(實例1)的大於1000小時之壽命相比，在電洞注入層中使用PEDOT/PSS之裝置(比較實例1)的壽命為46小時。下表1概述實例裝置之組成及效能特徵。 The devices of Example 1 and Comparative Example 1 were operated at DC current to produce an initial brightness of 1000 cd/m 2 . Here, the device lifetime is defined as the time at which the luminance decays to 80% of the initial level under constant DC drive at room temperature. The life of the apparatus using PEDOT/PSS in the hole injection layer (Comparative Example 1) was 46 hours as compared with the life of the apparatus using Compound 1 (Example 1) in the hole injection layer of more than 1000 hours. Table 1 below summarizes the composition and performance characteristics of the example devices.
表1及圖7展示在電洞注入層中使用化合物1代替PEDOT/PSS導致裝置之壽命意外劇烈增加，如圖4-6所示其與裝置效率及效能之小幅降低遠不成比例。 Tables 1 and 7 show that the use of Compound 1 in place of PEDOT/PSS in the hole injection layer caused an unexpectedly dramatic increase in the life of the device, as shown in Figure 4-6, which is far from proportional to the small reduction in efficiency and efficiency of the device.
除藉由旋塗0.75重量%之主體-1及摻雜劑顏料綠-1及顏料紅-1(比率為70：20：10)之溶液來沈積發射層以外，以與實例1相同之方式製造實例2之裝置。在DC電流下，實例2之裝置產生圖8中所示之發射光譜，其自發射層之紅摻雜劑具有位於約622nm處之峰。顯著缺少化合物1之任何磷光，其將在發射光譜之綠光區域中偵側到。此資料指示所有可偵測發射均係來自發射層且無一者來自電洞注入層中之化合物1。其他裝置效能資料係展示於圖9及10中。 The fabrication was carried out in the same manner as in Example 1 except that the emissive layer was deposited by spin coating 0.75 wt% of the bulk-1 and the dopant pigment green-1 and pigment red-1 (ratio 70:20:10) solution. The device of Example 2. At DC current, the device of Example 2 produced the emission spectrum shown in Figure 8, with the red dopant from the emissive layer having a peak at about 622 nm. There is a significant lack of any phosphorescence of Compound 1, which will be detected in the green light region of the emission spectrum. This data indicates that all detectable emissions are from the emission layer and none of them are from compound 1 in the hole injection layer. Other device performance data are shown in Figures 9 and 10.
以類似於比較實例1之裝置的方式製造實例3之裝置。歷時30秒 鐘自化合物2於苯甲醚中之0.5重量%溶液以4000rpm旋塗電洞注入層。在250℃下將薄膜烘焙30min。對於電洞傳輸層而言，歷時30秒鐘將1.0重量%之N4,N4'-二(萘-1-基)-N4,N4'-雙(4-乙烯基苯基)聯苯-4,4'-二胺於甲苯中之溶液以4000rpm旋塗至電洞注入層上。接著在200℃下於手套箱中之加熱板上將薄膜烘焙30分鐘。烘焙後薄膜變成不溶性薄膜。冷卻至室溫後，藉由歷時30秒鐘將0.75重量%之主體-1及顏料綠-2(主體與摻雜劑比率為88：12)之溶液以1000rpm旋塗至電洞傳輸層上來沈積發射層。接著將發射層在100℃下烘焙1小時。ETL1為5nm之2,3,6,7,10,11-六苯基苯幷菲(hexaphenyltriphenylene，HPT)且ETL2為45nm之Alq3，其兩者均藉由真空熱蒸發而沈積。除電洞注入材料為化合物1以外，以與實例3相同之方式製造實例4之裝置。 The apparatus of Example 3 was fabricated in a manner similar to that of Comparative Example 1. The hole injection layer was spin-coated at 4000 rpm from a 0.5 wt% solution of Compound 2 in anisole over 30 seconds. The film was baked at 250 ° C for 30 min. For the hole transport layer, 1.0% by weight of N 4 , N 4 '-bis(naphthalen-1-yl)-N 4 , N 4 '-bis(4-vinylphenyl) is bonded for 30 seconds. A solution of benzene-4,4'-diamine in toluene was spin-coated onto the hole injection layer at 4000 rpm. The film was then baked at 200 ° C for 30 minutes on a hot plate in a glove box. The film becomes an insoluble film after baking. After cooling to room temperature, a solution of 0.75 wt% of Host-1 and Pigment Green-2 (host to dopant ratio of 88:12) was spin coated onto the hole transport layer at 1000 rpm for 30 seconds. Emissive layer. The emissive layer was then baked at 100 ° C for 1 hour. ETL1 is 5 nm of 2,3,6,7,10,11-hexaphenyltriphenylene (HPT) and ETL2 is 45 nm of Alq 3 , both of which are deposited by vacuum thermal evaporation. The apparatus of Example 4 was fabricated in the same manner as in Example 3 except that the hole injection material was Compound 1.
如圖11-13中所示，在DC電流下運作裝置實例3及4且獲得效能資料。下表2概述裝置實例3及4之組成及效能特徵。 As shown in Figures 11-13, device examples 3 and 4 were operated at DC current and performance data was obtained. Table 2 below summarizes the composition and performance characteristics of device examples 3 and 4.
此資料證明在電洞注入層中使用化合物1之實例4裝置具有比在電洞注入層中使用化合物2之實例3裝置更佳的效能特徵。此比較證明可交聯銥錯合物上之不同間隔基可影響裝置效能。此效應可歸因於不 同間隔基具有不同之可撓性、幾何形狀、電化學性質或其對ITO陽極之影響(例如誘導ITO陽極上之表面偶極子)。 This data demonstrates that the Example 4 device using Compound 1 in the hole injection layer has better performance characteristics than the Example 3 device using Compound 2 in the hole injection layer. This comparison demonstrates that different spacers on the crosslinkable complex can affect device performance. This effect can be attributed to no The spacers have different flexibility, geometry, electrochemical properties or their effect on the ITO anode (eg, inducing surface dipoles on the ITO anode).
以下實例證明可藉由在電洞注入層中包括摻雜劑來進一步增強裝置效能。以類似於比較實例1之裝置的方式製造實例5之裝置。歷時30秒鐘自0.25重量%之95%化合物1及5%摻雜劑三苯甲基-肆(五氟苯基)硼酸鹽(CD1)於環己酮中之溶液以4000rpm旋塗電洞注入層。在250℃下將薄膜烘焙30min。對於電洞傳輸層而言，歷時30秒鐘將1.0重量%之N4,N4'-二(萘-1-基)-N4,N4'-雙(4-乙烯基苯基)聯苯-4,4'-二胺於甲苯中之溶液以4000rpm旋塗至電洞注入層上。接著在200℃下於手套箱中之加熱板上將薄膜烘焙30分鐘。烘焙後薄膜變成不溶性薄膜。冷卻至室溫後，藉由歷時30秒鐘將0.75重量%之主體-1及顏料綠-2(主體與摻雜劑比率為88：12)溶液以1000rpm旋塗至電洞傳輸層上來沈積發射層。接著將發射層在100℃下烘焙1小時。ETL1為5nm之2,3,6,7,10,11-六苯基苯幷菲(HPT)且ETL2為50nm之Alq3，其兩者均藉由真空熱蒸發而沈積。除用於電洞注入層之摻雜劑分別為4-異丙基-4'-甲基-二苯基錪(五氟苯基)硼酸鹽(CD2)及N,N-二甲基苯銨肆(五氟苯基)硼酸鹽(CD3)以外，以與實例5相同之方式製造實例6及7之裝置。 The following examples demonstrate that device performance can be further enhanced by including dopants in the hole injection layer. The apparatus of Example 5 was fabricated in a manner similar to that of Comparative Example 1. A solution of 95% Compound 1 and 5% dopant trityl-niobium (pentafluorophenyl) borate (CD1) in cyclohexanone at 4,000 rpm was spin-coated at 4000 rpm for 30 seconds. Floor. The film was baked at 250 ° C for 30 min. For the hole transport layer, 1.0% by weight of N 4 , N 4 '-bis(naphthalen-1-yl)-N 4 , N 4 '-bis(4-vinylphenyl) is bonded for 30 seconds. A solution of benzene-4,4'-diamine in toluene was spin-coated onto the hole injection layer at 4000 rpm. The film was then baked at 200 ° C for 30 minutes on a hot plate in a glove box. The film becomes an insoluble film after baking. After cooling to room temperature, a 0.75 wt% solution of Host-1 and Pigment Green-2 (host to dopant ratio of 88:12) was spin coated onto the hole transport layer at 1000 rpm for 30 seconds to deposit the emission. Floor. The emissive layer was then baked at 100 ° C for 1 hour. ETL1 is 5 nm of 2,3,6,7,10,11-hexaphenylbenziphenanthrene (HPT) and ETL2 is 50 nm of Alq 3 , both of which are deposited by vacuum thermal evaporation. The dopants used for the hole injection layer are 4-isopropyl-4'-methyl-diphenylphosphonium (pentafluorophenyl) borate (CD2) and N,N-dimethylanilinium, respectively. The apparatus of Examples 6 and 7 was produced in the same manner as in Example 5 except for ruthenium (pentafluorophenyl) borate (CD3).
如圖14-16中所示，在DC電流下運作裝置實例5-7且獲得效能資料。下表3概述裝置實例5-7之組成及效能特徵。此資料證明以導電性摻雜劑摻雜HIL可用來改良裝置之效能。舉例而言，此資料展示與實例3及4之在HIL中不具有摻雜劑之裝置相比，OLED裝置之運作電壓顯著降低且發光效率增加。此效應可歸因於導電性摻雜劑增強HIL中之電洞遷移率、改良ITO/HIL界面、改良電荷注入及/或促進可交聯銥錯合物之聚合作用的能力。 As shown in Figures 14-16, device examples 5-7 were operated at DC current and performance data was obtained. Table 3 below summarizes the composition and performance characteristics of device examples 5-7. This data demonstrates that doping HIL with a conductive dopant can be used to improve the performance of the device. For example, this data shows that the operating voltage of the OLED device is significantly reduced and the luminous efficiency is increased as compared to the devices of Examples 3 and 4 that do not have a dopant in the HIL. This effect can be attributed to the ability of the conductive dopant to enhance hole mobility in the HIL, improve the ITO/HIL interface, improve charge injection, and/or promote polymerization of the crosslinkable ruthenium complex.
以類似於比較實例1之裝置的方式製造實例8之裝置。歷時30秒鐘自0.25重量%之97%化合物2及3%摻雜劑三苯甲基-肆(五氟苯基)硼酸鹽(CD1)於環己酮中之溶液以4000rpm旋塗電洞注入層。在200℃下將薄膜烘焙30min。對於電洞傳輸層而言，歷時30秒鐘將1.0重量%之N4,N4'-二(萘-1-基)-N4,N4'-雙(4-乙烯基苯基)聯苯-4,4'-二胺於甲苯中之溶液以4000rpm旋塗至電洞注入層上。接著在200℃下於手套箱中之加熱板上將薄膜烘焙30分鐘。烘焙後薄膜變成不溶性薄膜。冷卻至室溫後，藉由歷時30秒鐘將0.75重量%之主體-2及顏料綠-2(主體與摻雜劑比率為88：12)溶液以1000rpm旋塗至電洞傳輸層上來沈積發射層。接著將發射層在100℃下烘焙1小時。ETL1為5nm之2,3,6,7,10,11-六苯基苯幷菲(HPT)且ETL2為50nm之Alq3，其兩者均藉由真空熱蒸發而沈積。使裝置實例8在DC電流下運作且獲得效能資料。裝置之組成及效能特徵概述於表4中。 The apparatus of Example 8 was fabricated in a manner similar to that of Comparative Example 1. A solution of 0.15% of compound 2 and 3% of the dopant trityl-niobium (pentafluorophenyl) borate (CD1) in cyclohexanone at 4,000 rpm for 30 seconds was spin-coated at 4000 rpm. Floor. The film was baked at 200 ° C for 30 min. For the hole transport layer, 1.0% by weight of N 4 , N 4 '-bis(naphthalen-1-yl)-N 4 , N 4 '-bis(4-vinylphenyl) is bonded for 30 seconds. A solution of benzene-4,4'-diamine in toluene was spin-coated onto the hole injection layer at 4000 rpm. The film was then baked at 200 ° C for 30 minutes on a hot plate in a glove box. The film becomes an insoluble film after baking. After cooling to room temperature, a 0.75 wt% solution of Host-2 and Pigment Green-2 (host to dopant ratio of 88:12) was spin coated onto the hole transport layer at 1000 rpm for 30 seconds to deposit emission. Floor. The emissive layer was then baked at 100 ° C for 1 hour. ETL1 is 5 nm of 2,3,6,7,10,11-hexaphenylbenziphenanthrene (HPT) and ETL2 is 50 nm of Alq 3 , both of which are deposited by vacuum thermal evaporation. Device Example 8 was operated at DC current and performance data was obtained. The composition and performance characteristics of the device are summarized in Table 4.
除使用7%之CD1作為導電性摻雜劑以外，以類似於實例8之裝置的方式製造實例9之裝置。裝置之效率高於裝置實例8之效率。使裝置實例9在DC電流下運作且獲得效能資料。裝置之組成及效能特徵概述於表4中。 The apparatus of Example 9 was fabricated in a manner similar to that of the apparatus of Example 8, except that 7% of CD1 was used as the conductive dopant. The efficiency of the device is higher than the efficiency of device example 8. Device Example 9 was operated at DC current and performance data was obtained. The composition and performance characteristics of the device are summarized in Table 4.
以類似於實例8之裝置的方式製造實例10之裝置。歷時30秒鐘自0.25重量%之90%化合物6及10%摻雜劑三苯甲基-肆(五氟苯基)硼酸鹽(CD1)於環己酮中之溶液以4000rpm旋塗電洞注入層。在200℃下將薄膜烘焙30min。對於電洞傳輸層而言，歷時30秒鐘將1.0重量%之N4,N4'-二(萘-1-基)-N4,N4'-雙(4-乙烯基苯基)聯苯-4,4'-二胺於甲苯中之溶液以4000rpm旋塗至電洞注入層上。接著在200℃下於手套箱中之加熱板上將薄膜烘焙30分鐘。烘焙後薄膜變成不溶性薄膜。冷卻至室溫後，藉由歷時30秒鐘將0.75重量%之主體-1及顏料綠-2(主體與摻雜劑比率為88：12)溶液以1000rpm旋塗至電洞傳輸層上來沈積發射層。接著將發射層在100℃下烘焙1小時。ETL1為5nm之2,3,6,7,10,11-六苯基苯幷菲(HPT)且ETL2為50nm之Alq3，其兩者均藉由真空熱蒸發而沈積。使裝置實例10在DC電流下運作且獲得效能資料。裝置之組成及效能特徵概述於表4中。 The apparatus of Example 10 was fabricated in a manner similar to the apparatus of Example 8. A solution of 90% compound 6 and 10% dopant trityl-niobium (pentafluorophenyl) borate (CD1) in cyclohexanone at 4,000 rpm for 30 seconds was spin-coated at 4000 rpm. Floor. The film was baked at 200 ° C for 30 min. For the hole transport layer, 1.0% by weight of N 4 , N 4 '-bis(naphthalen-1-yl)-N 4 , N 4 '-bis(4-vinylphenyl) is bonded for 30 seconds. A solution of benzene-4,4'-diamine in toluene was spin-coated onto the hole injection layer at 4000 rpm. The film was then baked at 200 ° C for 30 minutes on a hot plate in a glove box. The film becomes an insoluble film after baking. After cooling to room temperature, a 0.75 wt% solution of Host-1 and Pigment Green-2 (host to dopant ratio of 88:12) was spin coated onto the hole transport layer at 1000 rpm for 30 seconds to deposit the emission. Floor. The emissive layer was then baked at 100 ° C for 1 hour. ETL1 is 5 nm of 2,3,6,7,10,11-hexaphenylbenziphenanthrene (HPT) and ETL2 is 50 nm of Alq 3 , both of which are deposited by vacuum thermal evaporation. Device instance 10 was operated at DC current and performance data was obtained. The composition and performance characteristics of the device are summarized in Table 4.
除歷時30秒鐘自0.25重量%之95%化合物10及5%摻雜劑三苯甲基-肆(五氟苯基)硼酸鹽(CD1)於環己酮中之溶液以4000rpm旋塗電洞注入層以外，以類似於實例10之裝置的方式製造實例11之裝置。使裝置實例11在DC電流下運作且獲得效能資料。裝置之組成及效能特徵概述於表4中。 A solution of 95% compound 10 and 5% dopant trityl-niobium (pentafluorophenyl) borate (CD1) in cyclohexanone was spin-coated at 4000 rpm for 30 seconds. The apparatus of Example 11 was fabricated in a manner similar to the apparatus of Example 10, except for the injection layer. Device Example 11 was operated at DC current and performance data was obtained. The composition and performance characteristics of the device are summarized in Table 4.
除歷時30秒鐘自0.25重量%之95%化合物11及5%摻雜劑三苯甲基-肆(五氟苯基)硼酸鹽(CD1)於環己酮中之溶液以4000rpm旋塗電洞注入層以外，以類似於實例10之裝置的方式製造實例12之裝置。使裝置實例12在DC電流下運作且獲得效能資料。裝置之組成及效能特徵概 述於表4中。 A solution of 95% compound 11 and 5% dopant trityl-niobium (pentafluorophenyl) borate (CD1) in cyclohexanone was spin-coated at 4000 rpm for 30 seconds. The apparatus of Example 12 was fabricated in a manner similar to the apparatus of Example 10, except for the injection layer. Device instance 12 was operated at DC current and performance data was obtained. Device composition and performance characteristics It is described in Table 4.
除歷時30秒鐘自0.25重量%之95%化合物12及5%摻雜劑三苯甲基-肆(五氟苯基)硼酸鹽(CD1)於環己酮中之溶液以4000rpm旋塗電洞注入層以外，以類似於實例10之裝置的方式製造實例13之裝置。使裝置實例13在DC電流下運作且獲得效能資料。裝置之組成及效能特徵概述於表4中。 A solution of 95% compound 12 and 5% dopant trityl-niobium (pentafluorophenyl) borate (CD1) in cyclohexanone was sprayed at 4000 rpm for 30 seconds. The apparatus of Example 13 was fabricated in a manner similar to the apparatus of Example 10, except for the injection layer. Device instance 13 was operated at DC current and performance data was obtained. The composition and performance characteristics of the device are summarized in Table 4.
以類似於實例8之裝置的方式製造實例14之裝置。歷時30秒鐘自0.25重量%之95%化合物13及5%摻雜劑三苯甲基-肆(五氟苯基)硼酸鹽(CD1)於環己酮中之溶液以4000rpm旋塗電洞注入層。在225℃下將薄膜烘焙30min。對於電洞傳輸層而言，歷時30秒鐘將1.0重量%之N4,N4'-二(萘-1-基)-N4,N4'-雙(4-乙烯基苯基)聯苯-4,4'-二胺於甲苯中之溶液以4000rpm旋塗至電洞注入層上。接著在200℃下於手套箱中之加熱板上將薄膜烘焙30分鐘。烘焙後薄膜變成不溶性薄膜。冷卻至室溫後，藉由歷時30秒鐘將0.75重量%之主體-3及顏料綠-2(主體與摻雜劑比率為88：12)溶液以1000rpm旋塗至電洞傳輸層上來沈積發射層。接著將發射層在100℃下烘焙1小時。ETL1為5nm之2,3,6,7,10,11-六苯基苯幷菲(HPT)且ETL2為50nm之Alq3，其兩者均藉由真空熱蒸發而沈積。使裝置實例14在DC電流下運作且獲得效能資料。裝置之組成及效能特徵概述於表4中。 The apparatus of Example 14 was fabricated in a manner similar to the apparatus of Example 8. A solution of 95% Compound 13 and 5% dopant trityl-niobium (pentafluorophenyl) borate (CD1) in cyclohexanone at 4,000 rpm for 30 seconds was spin-coated at 4000 rpm. Floor. The film was baked at 225 ° C for 30 min. For the hole transport layer, 1.0% by weight of N 4 , N 4 '-bis(naphthalen-1-yl)-N 4 , N 4 '-bis(4-vinylphenyl) is bonded for 30 seconds. A solution of benzene-4,4'-diamine in toluene was spin-coated onto the hole injection layer at 4000 rpm. The film was then baked at 200 ° C for 30 minutes on a hot plate in a glove box. The film becomes an insoluble film after baking. After cooling to room temperature, a 0.75 wt% solution of Host-3 and Pigment Green-2 (host to dopant ratio of 88:12) was spin coated onto the hole transport layer at 1000 rpm for 30 seconds to deposit the emission. Floor. The emissive layer was then baked at 100 ° C for 1 hour. ETL1 is 5 nm of 2,3,6,7,10,11-hexaphenylbenziphenanthrene (HPT) and ETL2 is 50 nm of Alq 3 , both of which are deposited by vacuum thermal evaporation. Device instance 14 was operated at DC current and performance data was obtained. The composition and performance characteristics of the device are summarized in Table 4.
除歷時30秒鐘自0.25重量%之95%化合物14及5%摻雜劑三苯甲基-肆(五氟苯基)硼酸鹽(CD1)於環己酮中之溶液以4000rpm旋塗電洞注入層以外，以類似於實例14之裝置的方式製造實例15之裝置。在200℃下將HIL薄膜烘焙30min。使裝置實例15在DC電流下運作且獲得效能資料。裝置之組成及效能特徵概述於表4中。 A solution of 95% compound 14 and 5% dopant trityl-niobium (pentafluorophenyl) borate (CD1) in cyclohexanone was spin-coated at 4000 rpm for 30 seconds. The apparatus of Example 15 was fabricated in a manner similar to the apparatus of Example 14 except for the injection layer. The HIL film was baked at 200 ° C for 30 min. Device instance 15 was operated at DC current and performance data was obtained. The composition and performance characteristics of the device are summarized in Table 4.
除歷時30秒鐘自0.25重量%之95%化合物15及5%摻雜劑三苯甲基-肆(五氟苯基)硼酸鹽(CD1)於環己酮中之溶液以4000rpm旋塗電洞注 入層以外，以類似於實例14之裝置的方式製造實例16之裝置。使裝置實例16在DC電流下運作且獲得效能資料。裝置之組成及效能特徵概述於表4中。 A solution of 95% compound 15 and 5% dopant trityl-niobium (pentafluorophenyl) borate (CD1) in cyclohexanone was sprayed at 4000 rpm for 30 seconds. Note Outside of the layer, the apparatus of Example 16 was fabricated in a manner similar to the apparatus of Example 14. Device instance 16 was operated at DC current and performance data was obtained. The composition and performance characteristics of the device are summarized in Table 4.
以類似於實例8之裝置的方式製造實例17之裝置。歷時30秒鐘自0.25重量%之95%化合物16及5%摻雜劑三苯甲基-肆(五氟苯基)硼酸鹽(CD1)於環己酮中之溶液以4000rpm旋塗電洞注入層。在200℃下將薄膜烘焙30min。對於電洞傳輸層而言，歷時30秒鐘將1.0重量%之N4,N4'-二(萘-1-基)-N4,N4'-雙(4-乙烯基苯基)聯苯-4,4'-二胺於甲苯中之溶液以4000rpm旋塗至電洞注入層上。接著在200℃下於手套箱中之加熱板上將薄膜烘焙30分鐘。烘焙後薄膜變成不溶性薄膜。冷卻至室溫後，藉由歷時30秒鐘將0.75重量%之主體-4及顏料綠-2(主體與摻雜劑比率為88：12)溶液以1000rpm旋塗至電洞傳輸層上來沈積發射層。接著將發射層在100℃下烘焙1小時。ETL1為5nm之2,3,6,7,10,11-六苯基苯幷菲(HPT)且ETL2為50nm之Alq3，其兩者均藉由真空熱蒸發而沈積。使裝置實例17在DC電流下運作且獲得效能資料。裝置之組成及效能特徵概述於表4中。 The apparatus of Example 17 was fabricated in a manner similar to the apparatus of Example 8. A solution of 95% of compound 16 and 5% of the dopant trityl-niobium (pentafluorophenyl)borate (CD1) in cyclohexanone at 4,000 rpm for 30 seconds was spin-coated at 4000 rpm. Floor. The film was baked at 200 ° C for 30 min. For the hole transport layer, 1.0% by weight of N 4 , N 4 '-bis(naphthalen-1-yl)-N 4 , N 4 '-bis(4-vinylphenyl) is bonded for 30 seconds. A solution of benzene-4,4'-diamine in toluene was spin-coated onto the hole injection layer at 4000 rpm. The film was then baked at 200 ° C for 30 minutes on a hot plate in a glove box. The film becomes an insoluble film after baking. After cooling to room temperature, a 0.75 wt% solution of Host-4 and Pigment Green-2 (host to dopant ratio of 88:12) was spin coated onto the hole transport layer at 1000 rpm for 30 seconds to deposit the emission. Floor. The emissive layer was then baked at 100 ° C for 1 hour. ETL1 is 5 nm of 2,3,6,7,10,11-hexaphenylbenziphenanthrene (HPT) and ETL2 is 50 nm of Alq 3 , both of which are deposited by vacuum thermal evaporation. Device instance 17 was operated at DC current and performance data was obtained. The composition and performance characteristics of the device are summarized in Table 4.
本發明之某些可交聯銥錯合物係表示為Ir(L1)x(L2)y之雜片段銥錯合物，其中L1及L2為不同之C-Ir-N環金屬化有機配位子。該等雜片段金屬錯合物可利用不同配位子所賦予之理想特性。 Certain crosslinkable ruthenium complexes of the present invention are represented by a heterozygous complex of Ir(L 1 ) x (L 2 ) y wherein L 1 and L 2 are different C-Ir-N ring metals. Organic ligands. These hetero-fragment metal complexes can utilize the desirable properties imparted by different ligands.
舉例而言，認為含有Ir(L1)3作為發射體之電致磷光裝置比含有Ir(L2)3作為發射體之裝置更穩定，儘管兩個裝置發射類似色彩。但若L1具有比L2高之分子量，則Ir(L1)3將要求比Ir(L2)3高之真空蒸發溫度，因此降低使用Ir(L1)3之吸引力。在此情況下，雜片段Ir(L1)(L2)2或Ir(L1)2(L2)錯合物可具有由各配位子所賦予之理想特徵(亦即L1賦予良好穩定性，而L2賦予降低之分子量及較低之蒸發溫度)。 By way of example, that contains Ir (L 1) 3 as the phosphorescent emitter electrically ratio device comprising Ir (L 2) 3 is more stable as the emitter means, although the means for transmitting two similar colors. However, if L 1 has a molecular weight higher than L 2 , Ir(L 1 ) 3 will require a vacuum evaporation temperature higher than Ir(L 2 ) 3 , thus reducing the attractive force of using Ir(L 1 ) 3 . In this case, the hetero-fragment Ir(L 1 )(L 2 ) 2 or Ir(L 1 ) 2 (L 2 ) complex may have desirable characteristics imparted by each of the ligands (ie, L 1 is well-proportioned) Stability, while L 2 gives a reduced molecular weight and a lower evaporation temperature).
又，在另一情況下，若Ir(L1)3不溶而Ir(L2)3可溶於大多數有機溶劑，則Ir(L1)3不能用於諸如噴墨印刷之基於溶液的裝置製造方法。在此情況下，雜片段Ir(L1)(L2)2或Ir(L1)2(L2)錯合物可具有良好穩定性(如 由L1所賦予)及良好溶解性(如由L2所賦予)。 Also, in another case, if Ir(L 1 ) 3 is insoluble and Ir(L 2 ) 3 is soluble in most organic solvents, Ir(L 1 ) 3 cannot be used in a solution-based device such as inkjet printing. Production method. In this case, the hetero-fragment Ir(L 1 )(L 2 ) 2 or Ir(L 1 ) 2 (L 2 ) complex may have good stability (as conferred by L 1 ) and good solubility (eg Granted by L 2 ).
儘管雜片段金屬錯合物可具有此等優勢，但製造該等雜片段錯合物可具有挑戰性。一個問題在於在合成過程期間爭奪配位子，此產生Ir(L1)(L2)2與Ir(L1)2(L2)且甚至Ir(L1)3與Ir(L2)3之混合物。使用諸如管柱層析、昇華或再結晶之習知分離技術可能難以分離該混合物之各組份。因此，需要一種改良之製造雜片段金屬錯合物的方法。 While hetero-fragment metal complexes can have these advantages, making such hetero-fragment complexes can be challenging. One problem is that it competes for a ligand during the synthesis process, which produces Ir(L 1 )(L 2 ) 2 and Ir(L 1 ) 2 (L 2 ) and even Ir(L 1 ) 3 and Ir(L 2 ) 3 a mixture. It may be difficult to separate the components of the mixture using conventional separation techniques such as column chromatography, sublimation or recrystallization. Therefore, there is a need for an improved process for making hetero-fragment metal complexes.
因此，在另一態樣中，本發明提供具有分離增強官能基之雜片段金屬錯合物，該官能基以使得不同金屬錯合物可藉由諸如管柱層析的習知分離技術分離之方式區分混合物中之雜片段金屬錯合物。分離增強官能基係用以產生具有式M(L1)(LB)2或M(L1)2(LB)之金屬錯合物，其中M為金屬原子，其中L1及LB為與金屬M配位之不同配位子，且其中LB包括分離增強官能基。 Thus, in another aspect, the present invention provides a hetero-fragment metal complex having isolated enhanced functional groups such that different metal complexes can be separated by conventional separation techniques such as column chromatography. The manner distinguishes the hetero-fragment metal complex in the mixture. Separating the reinforcing functional group to produce a metal complex having the formula M(L 1 )(L B ) 2 or M(L 1 ) 2 (L B ), wherein M is a metal atom, wherein L 1 and L B are A different ligand coordinated to the metal M, and wherein L B includes a separation enhancing functional group.
可自含有具有式M(L1)(LA)2之金屬錯合物及具有式M(L1)2(LA)之金屬錯合物的混合物產生具有式M(L1)(LB)2或M(L1)2(LB)之此等金屬錯合物，其中L1及LA為與金屬原子M配位之不同配位子。配位子LA包括至少一個含有鹵素之基團。如本文中所用，"含有鹵素之基團"係指F、Cl、Br或I或含有F、Cl、Br或I中之至少一者的官能基。藉由以分離增強官能基取代LA配位子上之含有鹵素之基團，形成含有金屬錯合物M(L1)(LB)2或M(L1)2(LB)之第二混合物。分離且隔離後，可使金屬錯合物M(L1)(LB)2或M(L1)2(LB)經受進一步反應(例如交叉偶合、去保護、縮合、裂解或醯化)以製備其他雜片段金屬錯合物，諸如作為磷光發射體或電洞傳輸材料之彼等雜片段金屬錯合物。 A mixture of a metal complex having a formula M(L 1 )(L A ) 2 and a metal complex having the formula M(L 1 ) 2 (L A ) can be produced having the formula M(L 1 )(L) B ) 2 or M(L 1 ) 2 (L B ) of such metal complexes, wherein L 1 and L A are different ligands coordinated to the metal atom M. The ligand L A includes at least one group containing a halogen. As used herein, "halogen-containing group" refers to F, Cl, Br or I or a functional group containing at least one of F, Cl, Br or I. Forming a metal-containing complex M(L 1 )(L B ) 2 or M(L 1 ) 2 (L B ) by substituting a halogen-containing group on the L A ligand with an isolated reinforcing functional group Two mixtures. After separation and isolation, the metal complex M(L 1 )(L B ) 2 or M(L 1 ) 2 (L B ) can be subjected to further reactions (eg, cross-coupling, deprotection, condensation, cleavage or deuteration) To prepare other hetero-fragment metal complexes, such as their hetero-fragment metal complexes as phosphorescent emitters or hole transport materials.
舉例而言，當2-(聯苯-3-基)吡啶及2-苯基吡啶與Ir(acac)3反應時，以視兩個配位子之饋入比而定之比率形成I-A、I-B、I-C及I-D之混合物。因為其配位子具有類似極性，所以該4種組份並不易於藉由管柱層析而分離。 For example, when 2-(biphenyl-3-yl)pyridine and 2-phenylpyridine are reacted with Ir(acac) 3 , IA, IB, etc. are formed at a ratio depending on the feed ratio of the two ligands. A mixture of IC and ID. Because their ligands have similar polarities, the four components are not easily separated by column chromatography.
為製備純化合物I-B，首先藉由使Ir(PPy)3與1當量之N-溴代丁二醯亞胺(NBS)反應來製備溴化Ir(PPy)3之混合物。獲得未反應Ir(PPy)3、單溴Ir(PPy)3(II-A)及二溴Ir(PPy)3(II-B)之混合物。為增加不同金屬錯合物之間的極性差異，將頻哪醇基硼酸酯基(充當分離增強官能基)引入金屬錯合物中。藉由該反應，將金屬錯合物轉化成其相應硼酸酯III-A及III-B，其更易於藉由管柱層析而分離。隨後可將硼酸酯金屬錯合物III-A及III-B分別轉化成金屬錯合物I-B及I-C。過程展示如下。 To prepare the pure compound IB, a mixture of brominated Ir(PPy) 3 was first prepared by reacting Ir(PPy) 3 with 1 equivalent of N-bromosuccinimide (NBS). A mixture of unreacted Ir(PPy) 3 , monobromo Ir(PPy) 3 (II-A) and dibromoIr(PPy) 3 (II-B) was obtained. To increase the difference in polarity between the different metal complexes, a pinacolyl boronate group (acting as a separation enhancing functional group) is introduced into the metal complex. By this reaction, the metal complex is converted to its corresponding boronate esters III-A and III-B, which are more easily separated by column chromatography. The borate metal complexes III-A and III-B can then be converted to the metal complexes IB and IC, respectively. The process is shown below.
亦可使用其他分離增強官能基，包括具有三氟甲磺酸酯基、三 甲基矽烷基或胺基之彼等分離增強官能基。使用三氟甲磺酸酯基作為分離增強官能基之實例展示如下。 Other separation enhancing functional groups may also be used, including having a triflate group, three The separation of the methyl decyl or amine groups enhances the functional groups. An example using a triflate group as a separation enhancing functional group is shown below.
使用TMS作為分離增強官能基之實例展示如下。 An example of using TMS as a separation enhancing functional group is shown below.
製備雜片段金屬錯合物之此方法可用於製備本發明之可交聯金 屬錯合物。以下證明此方法用於合成如上所述之化合物1的用途。 This method of preparing a hetero-fragment metal complex can be used to prepare the cross-linkable gold of the present invention Is a complex compound. The use of this method for the synthesis of Compound 1 as described above is demonstrated below.
溴化混合物之合成：在排除光之情況下，將2.53g(14.2mmol)N-溴代丁二醯亞胺於200ml二氯甲烷中之溶液逐滴添加至9.3g(14.2mmol)面-參[2-(2-吡啶基-κN)苯基-κC]銥(III)於2300ml二氯甲烷中之有效攪拌溶液中。將溶液在室溫下進一步攪拌15小時。在減壓下濃縮至200ml之體積後，將溶液與1000ml乙醇混合。隨後，濾出微晶沈澱物，以100ml乙醇洗滌3次且接著在減壓下乾燥。獲得9.3g產物(溴化混合物)。溴化混合物含有約80%之單溴產物，10%之起始物質及10%之二溴產物。 Synthesis of bromination mixture: 2.53 g (14.2 mmol) of N-bromosuccinimide in 200 ml of dichloromethane was added dropwise to 9.3 g (14.2 mmol) of noodle-parameter in the absence of light. [2-(2-Pyridyl-κN)phenyl-κC] ruthenium (III) was effectively stirred in 2300 ml of dichloromethane. The solution was further stirred at room temperature for 15 hours. After concentrating to a volume of 200 ml under reduced pressure, the solution was mixed with 1000 ml of ethanol. Subsequently, the crystallite precipitate was filtered off, washed 3 times with 100 ml of ethanol and then dried under reduced pressure. 9.3 g of product (bromination mixture) were obtained. The brominated mixture contained about 80% monobrominated product, 10% starting material and 10% dibrominated product.
溴化混合物Brominated mixture
胺基中間物之合成：面-雙[2-(2-吡啶基-κN)苯基-κC]-[2-(2-吡啶基-κN)-(5-(4-胺基苯基)苯基)-κC]銥(III)。將2.0g上述溴化混合物、0.9g(4.1mmol)4-(4,4,5,5-四甲基-1,3,2-二氧雜硼-2-基)苯胺、1.0g(7mmol)碳酸鉀、500mg甲苯、100ml乙醇及50ml水混合且以氮淨化10分鐘。接著向混合物中添加0.3g Pd(PPh3)4。將混合物加熱至回流，歷時30小時。將混合物冷卻至室溫且分離有機層。在減壓下蒸發溶劑且在管柱中使用二氯甲烷作為溶離劑純化殘餘物。獲得1.2g單胺基產物。 Synthesis of amino intermediates: face-bis[2-(2-pyridyl-κN)phenyl-κC]-[2-(2-pyridyl-κN)-(5-(4-aminophenyl) Phenyl)-κC]铱(III). 2.0 g of the above brominated mixture, 0.9 g (4.1 mmol) of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaboron 2-Benzyl)aniline, 1.0 g (7 mmol) of potassium carbonate, 500 mg of toluene, 100 ml of ethanol and 50 ml of water were mixed and purified with nitrogen for 10 minutes. Next, 0.3 g of Pd(PPh 3 ) 4 was added to the mixture. The mixture was heated to reflux for 30 hours. The mixture was cooled to room temperature and the organic layer was separated. The solvent was evaporated under reduced pressure and the residue was purified using methylene chloride as solvent. 1.2 g of monoamine based product were obtained.
化合物1之合成：在氮下將1.0g(1.34mmol)面-雙[2-(2-吡啶基-κN)苯基-κC]-[2-(2-吡啶基-κN)-(5-(4-胺基苯基)苯基)-κC]銥(III)(上述胺基中間物)、0.49g(2.68mmol)4-溴苯乙烯、9mg乙酸鈀、0.08ml於甲苯中之1M三-第三丁基膦、0.39g(4.0mmol)第三丁醇鈉及100ml對二甲苯加熱至110℃，歷時6小時。冷卻至室溫後，將反應混合物傾入500ml甲醇中。收集沈澱物且在管柱中使用甲苯作為溶離劑純化。在純化後獲得0.36g產物(化合物1)。 Synthesis of Compound 1 : 1.0 g (1.34 mmol) of face-bis[2-(2-pyridyl-κN)phenyl-κC]-[2-(2-pyridyl-κN)-(5- (4-Aminophenyl)phenyl)-κC] ruthenium (III) (the above amino intermediate), 0.49 g (2.68 mmol) of 4-bromostyrene, 9 mg of palladium acetate, 0.08 ml of 1 M in toluene - Tributylphosphine, 0.39 g (4.0 mmol) of sodium tributoxide and 100 ml of p-xylene were heated to 110 ° C for 6 hours. After cooling to room temperature, the reaction mixture was poured into 500 ml of methanol. The precipitate was collected and purified using toluene as a dissolving agent in the column. After purification, 0.36 g of product (Compound 1) was obtained.
雜片段金屬錯合物I-B及I-C之合成：
酸酯係如下合成：
I-B之合成：在三頸燒瓶中混合1.5g(1.92mmol)上述酸酯、0.45g(2.88mmol)溴苯、58mg(0.12mmol)S-Phos、1.2g(5.7mmol)磷酸鉀、80ml甲苯與8ml水。將混合物以氮鼓泡20min。向脫氣混合物中添加0.03g(0.03mmol)Pd2(dba)3。在氮氣氛下使反應回流2小時。冷卻至室溫後，經由矽藻土床過濾反應混合物。以二氯甲烷洗滌矽藻土床上之黃色沈澱物。將二氯甲烷溶液與甲苯溶液合併。以硫酸鎂乾燥溶液。溶劑蒸發後，藉由管柱使用1：1之己烷與二氯甲烷作為溶離劑純化殘餘物。獲得1.2g純產物(I-B)。在高真空下在275℃下使最終產物昇華。 Synthesis of IB: 1.5 g (1.92 mmol) of the above was mixed in a three-necked flask The acid ester, 0.45 g (2.88 mmol) of bromobenzene, 58 mg (0.12 mmol) of S-Phos, 1.2 g (5.7 mmol) of potassium phosphate, 80 ml of toluene and 8 ml of water. The mixture was bubbled with nitrogen for 20 min. To the degassed mixture was added 0.03 g (0.03 mmol) of Pd 2 (dba) 3 . The reaction was refluxed for 2 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture was filtered through a pad of Celite. The yellow precipitate on the bed of diatomaceous earth was washed with dichloromethane. The dichloromethane solution was combined with the toluene solution. The solution was dried over magnesium sulfate. After evaporation of the solvent, the residue was purified by column using 1:1 hexanes and dichloromethane as solvent. 1.2 g of pure product (IB) were obtained. The final product was sublimed at 275 ° C under high vacuum.
雜片段金屬錯合物I-C之合成(以與I-B相同之方式)。 Synthesis of the heterozygous metal complex I-C (in the same manner as I-B).
雜片段金屬錯合物IV-A及IV-B之合成：將6.3g溴化Ir(PPy)3混合物置入三頸燒瓶中。接著向此燒瓶中添加2.4g(12.3mmol)3-三甲基矽烷基苯基酸、0.2g(0.49mmol)S-Phos、2.8g(12.3mmol)磷酸鉀、600ml甲苯及60ml水。將混合物脫氣20min。添加0.11g(0.12mmol)Pd2(dba)3。在氮下將混合物加熱至回流隔夜。藉由分離有機層且蒸發溶劑處理反應。藉由管柱層析使用1：1之己烷與二氯甲烷作為溶離劑純化殘餘物。獲得1.3g IV-A及2g IV-B。 Synthesis of hetero-fragment metal complexes IV-A and IV-B: 6.3 g of a mixture of brominated Ir(PPy) 3 was placed in a three-necked flask. Next, 2.4 g (12.3 mmol) of 3-trimethyldecylphenyl group was added to the flask. Acid, 0.2 g (0.49 mmol) of S-Phos, 2.8 g (12.3 mmol) of potassium phosphate, 600 ml of toluene and 60 ml of water. The mixture was degassed for 20 min. 0.11 g (0.12 mmol) of Pd 2 (dba) 3 was added . The mixture was heated to reflux overnight under nitrogen. The reaction was treated by separating the organic layer and evaporating the solvent. The residue was purified by column chromatography using 1:1 hexanes and dichloromethane as solvent. 1.3 g IV-A and 2 g IV-B were obtained.
I-B(上述)之合成：可藉由使用Y.Zafrani,E.Gershonov及I.Columbus,"Efficient and Facile Ar-Si Bond Cleavage by Montmorillonite KSF：Synthetic and Mechanistic Aspects of Solvent-Free Protodesilylation Studied by Solution and Solid-State MAS NMR",J.Org.Chem.，第72(18)卷，第7014-7017頁(2007)中揭示之方法自IV-A裂解TMS基團來合成I-B。 Synthesis of IB (above): by using Y. Zafrani, E. Gershonov and I. Columbus, "Efficient and Facile Ar-Si Bond Cleavage by Montmorillonite KSF: Synthetic and Mechanistic Aspects of Solvent-Free Protodesilylation Studied by Solution and Solid -State MAS NMR", J. Org. Chem. , Vol. 72 (18), pp. 7014-7017 (2007). The method of synthesizing IB from IV-A to cleave TMS groups.
I-C(上述)之合成：可藉由按照上文提及之參考文獻中揭示之方法自IV-B裂解TMS基團來合成I-C。 Synthesis of I-C (described above): I-C can be synthesized by cleavage of a TMS group from IV-B according to the method disclosed in the above-referenced references.
化合物V之合成：
氯化中間物之合成：將5g(29.8mmol)2-甲基-6-苯基吡啶及4.8g(13mmol)氯化銥(IrCL3˙H2O)一起添加至以35mL 2-乙氧基乙醇及8mL H2O作為溶劑之燒瓶中。將溶液加熱至回流，歷時24小時且濾出紅色沈澱產物且以甲醇洗滌。產物不經進一步純化即使用。收集到4.2g(3.7mmol)中間物A。 Synthesis of chlorinated intermediate: 5 g (29.8 mmol) of 2-methyl-6-phenylpyridine and 4.8 g (13 mmol) of cesium chloride (IrCL 3 ̇H 2 O) were added together to 35 mL of 2-ethoxyl Ethanol and 8 mL of H 2 O were used as a solvent in a flask. The solution was heated to reflux over 24 hours and the red precipitated product was filtered and washed with methanol. The product was used without further purification. 4.2 g (3.7 mmol) of Intermediate A was collected.
氯化中間物Chlorinated intermediate
溴化混合物之合成：將3.4g(3.01mmol)上述氯化中間物、1.55g(6.6mmol)2-(3-溴苯基)吡啶及1.54g(6.02mmol)三氟甲烷磺酸銀(AgOTf)一起稱量至以約70mL 2-乙氧基乙醇作為溶劑之燒瓶中。將溶液加熱至回流，歷時18小時且使產物在甲醇中沈澱並過濾。將粗中間物乾燥裝填於矽藻土上且藉由管柱層析使用己烷/二氯甲烷作為溶離劑純化。收集到1.3g(1.7mmol)溴化混合物。 Synthesis of bromination mixture: 3.4 g (3.01 mmol) of the above chlorinated intermediate, 1.55 g (6.6 mmol) of 2-(3-bromophenyl)pyridine and 1.54 g (6.02 mmol) of silver trifluoromethanesulfonate (AgOTf) ) Weighed together into a flask containing about 70 mL of 2-ethoxyethanol as a solvent. The solution was heated to reflux for 18 hours and the product was taken up in methanol and filtered. The crude intermediate was dried and loaded onto celite and purified by column chromatography using hexane/dichloromethane as solvent. A 1.3 g (1.7 mmol) bromination mixture was collected.
溴化混合物Brominated mixture
酸酯之合成：將1.3g上述溴化混合物、0.86g(3.4mmol)雙(頻哪醇根基)二硼、0.042g(0.051mmol)Pd(dppf)2Cl2及0.5g(5.1mmol)乙酸鉀稱量至使用二噁烷作為溶劑之燒瓶中。將溶液以氮淨化且加熱至90℃，歷時12小時。藉由旋轉蒸發移除二噁烷；將固體溶解於二氯甲烷中且以水洗滌。藉由旋轉蒸發移除二氯甲烷且將物質乾燥裝填於矽藻土上且藉由管柱層析使用己烷/二氯甲烷作為溶離劑純化。收集到0.52g(0.64mmol)所需之單酸酯化合物。 Synthesis of the acid ester: 1.3 g of the above brominated mixture, 0.86 g (3.4 mmol) of bis(pinacolyl)diboron, 0.042 g (0.051 mmol) of Pd(dppf) 2 Cl 2 and 0.5 g (5.1 mmol) of acetic acid Potassium was weighed into a flask using dioxane as a solvent. The solution was purged with nitrogen and heated to 90 ° C for 12 hours. The dioxane was removed by rotary evaporation; the solid was dissolved in dichloromethane and washed with water. Dichloromethane was removed by rotary evaporation and the material was dried and applied to celite and purified by column chromatography using hexane/dichloromethane as solvent. Collected 0.52g (0.64mmol) of the required single Acid ester compound.
酸酯 Acid ester
化合物V之合成：將0.52g(0.64mmol)上述單酸酯、0.3g(1.93mmol)苯基酸、0.006g(0.0064mmol)參(二亞苄基丙酮)二鈀(0)[Pd2(dba)3]、0.10g(0.025mmol)2-二環己基膦基-2',6'-二甲氧基聯苯(SPhos)及0.4g(1.92mmol)磷酸三鉀(K3PO4)稱量至燒瓶中。使用30mL甲苯及10mL水作為溶劑且將溶液以氮淨化。將溶液加熱至回流，歷時12小時。冷卻後，分離有機層且以MgSO4乾燥。藉由管柱層析使用己烷/二氯甲烷作為溶離劑分離產物。藉由旋轉蒸發移除溶劑且在真空下乾燥產物。藉由在250℃下高真空昇華進一步純化產物，得到0.3g(0.39mmol)。 Synthesis of Compound V: 0.52 g (0.64 mmol) of the above single Acid ester, 0.3 g (1.93 mmol) phenyl Acid, 0.006 g (0.0064 mmol) ginsyl (dibenzylideneacetone) dipalladium (0) [Pd 2 (dba) 3 ], 0.10 g (0.025 mmol) 2-dicyclohexylphosphino-2', 6'- Dimethoxybiphenyl (SPhos) and 0.4 g (1.92 mmol) of tripotassium phosphate (K 3 PO 4 ) were weighed into the flask. 30 mL of toluene and 10 mL of water were used as a solvent and the solution was purged with nitrogen. The solution was heated to reflux for 12 hours. After cooling, the organic layer was separated and dried in MgSO 4. The product was isolated by column chromatography using hexane/dichloromethane as the solvent. The solvent was removed by rotary evaporation and the product was dried under vacuum. The product was further purified by high vacuum sublimation at 250 ° C to give 0.3 g (0.39 mmol).
化合物VCompound V
化合物VI之合成： Synthesis of Compound VI:
製備2-溴吡啶(40g，253mmol)、3-溴苯基酸(61.0g，303.8mmol)、三苯基膦(6.64g，25.3mmol)、碳酸鉀(87.4g，632.5mmol)於300mL二甲氧基乙烷及200mL水中之混合物。歷時20分鐘將氮直接鼓泡進入混合物中，接著添加乙酸鈀(2.84g，12.65mmol)。在氮下將反應混合物加熱至回流。此日結束時，藉由TLC偵測到痕量2-溴吡啶。因此添加額外10公克之2-溴苯基酸且使反應持續至回流隔夜。冷卻反應混合物且連同乙酸乙酯一起添加水。將各層分離且將含水層以乙酸乙酯萃取。將有機層經硫酸鎂乾燥、過濾且蒸發成棕色油狀物。藉由管柱層析以0至40%乙酸乙酯/己烷溶離，繼而在真空下蒸餾來純化油狀物。如由GC-MS所證實獲得45.1g所需產物(52%產率)。 Preparation of 2-bromopyridine (40 g, 253 mmol), 3-bromophenyl A mixture of acid (61.0 g, 303.8 mmol), triphenylphosphine (6.64 g, 25.3 mmol), potassium carbonate (87.4 g, 632.5 mmol) in 300 mL dimethoxyethane and 200 mL water. Nitrogen was bubbled directly into the mixture over 20 minutes, followed by the addition of palladium acetate (2.84 g, 12.65 mmol). The reaction mixture was heated to reflux under nitrogen. At the end of the day, traces of 2-bromopyridine were detected by TLC. So add an extra 10 grams of 2-bromophenyl The acid was allowed to continue until reflux overnight. The reaction mixture was cooled and water was added along with ethyl acetate. The layers were separated and the aqueous layer was extracted with ethyl acetate. The organic layer was dried with MgSO4, filtered and evaporated The oil was purified by column chromatography eluting with 0 to 40% ethyl acetate / hexanes and then distilled under vacuum. 45.1 g of the desired product (52% yield) was obtained as confirmed by GC-MS.
製備2-(3-溴苯基)吡啶(12.2g，52.10mmol)、3-(4,4,5,5-四甲基-1,3,2-二氧雜硼-2-基)苯酚(13.76g，62.53mmol)、2-二環己基膦基-2',6'-二甲氧基聯苯(856mg，2.08mmol)、磷酸三鉀單水合物(36g，156.3mmol)於180mL二噁烷及18mL水中之混合物。歷時20分鐘將氮直接鼓泡進入混合物中，接著添加參(二亞苄基丙酮)二鈀(0)(477 mg，0.52mmol)。在氮下在100℃下將反應混合物加熱3小時，接著使其冷卻至室溫隔夜。將水添加至反應混合物中且以乙酸乙酯將混合物萃取3次。經硫酸鎂乾燥有機萃取物、過濾且蒸發為殘餘物。藉由管柱層析以20%及40%之乙酸乙酯/己烷溶離純化殘餘物。如由GC-MS所證實獲得12.5g黃色油狀物(97%產率)。 Preparation of 2-(3-bromophenyl)pyridine (12.2 g, 52.10 mmol), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaboron 2-yl)phenol (13.76 g, 62.53 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (856 mg, 2.08 mmol), tripotassium phosphate monohydrate (36 g, A mixture of 156.3 mmol) in 180 mL of dioxane and 18 mL of water. Nitrogen was bubbled directly into the mixture over 20 minutes, followed by the addition of bis(dibenzylideneacetone)dipalladium(0) (477 mg, 0.52 mmol). The reaction mixture was heated at 100 ° C for 3 hours under nitrogen then cooled to room temperature overnight. Water was added to the reaction mixture and the mixture was extracted 3 times with ethyl acetate. The organic extract was dried over MgSO.sub.4, filtered and evaporated. The residue was purified by column chromatography eluting with 20% and 40% ethyl acetate/hexane. 12.5 g of a yellow oil (97% yield) was obtained as confirmed by GC-MS.
在0℃下，在500ml圓瓶燒瓶中混合12.5公克(50.6mmol)3'-(吡啶-2-基)聯苯-3-酚、12ml吡啶及約200ml二氯甲烷。向該混合物中添加14.3公克(101.2mmol)三氟乙酸酐且在0℃下攪拌30min，接著在室溫下攪拌1小時。將反應混合物以水洗滌數次。如由GC-MS所證實，蒸發溶劑後獲得約19公克(約100%產率)三氟甲磺酸酯。 12.5 g (50.6 mmol) of 3'-(pyridin-2-yl)biphenyl-3-phenol, 12 ml of pyridine and about 200 ml of dichloromethane were mixed in a 500 ml round flask at 0 °C. To the mixture was added 14.3 g (101.2 mmol) of trifluoroacetic anhydride and stirred at 0 ° C for 30 min, followed by stirring at room temperature for 1 hour. The reaction mixture was washed several times with water. As evidenced by GC-MS, about 19 grams (about 100% yield) of the triflate was obtained after evaporation of the solvent.
將8.8g(23.2mmol)三氟甲烷磺酸3'-(吡啶-2-基)聯苯-3-基酯、4.7g(46mmol)異丁烷酸、211mg Pd2(dba)3(0.23mmol)、396mg(0.965mmol)S-Phos、16.7公克(72.6mmol)K3PO4H2O及300ml甲苯饋入500ml圓形瓶燒瓶中。在攪拌下在氮下將反應混合物加熱至回流隔夜。藉由矽膠層析法以於己烷中之10%(v/v)乙酸乙酯作為溶離劑純化反應混合物。如由GC-MS所證實獲得約5.8公克固體(產率87%)產物。 8.8 g (23.2 mmol) of 3'-(pyridin-2-yl)biphenyl-3-yl trifluoromethanesulfonate, 4.7 g (46 mmol) of isobutane Acid, 211 mg of Pd 2 (dba) 3 (0.23 mmol), 396 mg (0.965 mmol) of S-Phos, 16.7 g (72.6 mmol) of K 3 PO 4 H 2 O and 300 ml of toluene were fed into a 500 ml round flask. The reaction mixture was heated to reflux under nitrogen with stirring overnight. The reaction mixture was purified by gelatin chromatography using 10% (v/v) ethyl acetate in hexanes as a solvent. Approximately 5.8 grams of solid (yield 87%) of the product was obtained as confirmed by GC-MS.
將3.4公克(11.8mmol)2-(3'-異丁基聯苯-3-基)吡啶、2.0公克(5.3mmol)IrCL3.3H2O及150ml溶劑混合物(2乙氧基乙醇/水：3：1)饋入250ml圓形瓶燒瓶中。在氮下將反應混合物加熱至回流隔夜。冷卻反應混合物且添加約100ml甲醇，接著過濾。以甲醇洗滌固體且乾燥。獲得約3.85公克氯-橋接銥二聚體且不經進一步純化即用於下一步驟。 3.4 g (11.8 mmol) of 2-(3'-isobutylbiphenyl-3-yl)pyridine, 2.0 g (5.3 mmol) of IrCL 3 .3H 2 O and 150 ml of a solvent mixture (2 ethoxyethanol/water: 3:1) Feed into a 250 ml round bottle flask. The reaction mixture was heated to reflux overnight under nitrogen. The reaction mixture was cooled and about 100 ml of methanol was added, followed by filtration. The solid was washed with methanol and dried. Approximately 3.85 grams of the chloro-bridged oxime dimer was obtained and used in the next step without further purification.
製備2-溴吡啶(8.66g，54.8mmol)、3-甲氧基苯基酸(10g，65.8mmol)、三苯基膦(1.44g，5.48mmol)、碳酸鉀(18.9g，137mmol)於100mL二甲氧基乙烷及66mL水中之混合物。歷時20分鐘將氮直接鼓泡進入混合物中，接著添加乙酸鈀(0.61g，2.74mmol)。在氮下將反應混合物加熱至回流隔夜。冷卻反應混合物且連同乙酸乙酯一起添加水。將各層分離且將含水層以乙酸乙酯萃取。經硫酸鎂乾燥有機層、過濾且蒸發至殘餘物。藉由管柱層析以0至20%之乙酸乙酯/己烷溶離純化殘餘物。如由GC-MS所證實獲得9.7g澄清油狀物(96%產率)。 Preparation of 2-bromopyridine (8.66 g, 54.8 mmol), 3-methoxyphenyl A mixture of acid (10 g, 65.8 mmol), triphenylphosphine (1.44 g, 5.48 mmol), potassium carbonate (18.9 g, 137 mmol) in 100 mL dimethoxyhexane and 66 mL water. Nitrogen was bubbled directly into the mixture over 20 minutes followed by the addition of palladium acetate (0.61 g, 2.74 mmol). The reaction mixture was heated to reflux overnight under nitrogen. The reaction mixture was cooled and water was added along with ethyl acetate. The layers were separated and the aqueous layer was extracted with ethyl acetate. The organic layer was dried over MgSO4, filtered and evaporatedEtOAc. The residue was purified by column chromatography eluting with 0 to 20% ethyl acetate /hexane. 9.7 g of a clear oil (96% yield) was obtained as confirmed by GC-MS.
製備2-(3-甲氧基苯基)吡啶(9.7g，52.37mmol)與鹽酸吡啶(72.6g，628.44mmol)之混合物。將混合物加熱至220℃。反應進行2小時。將水添加至冷卻混合物中且接著以二氯甲烷萃取兩次。經硫酸鎂乾燥有機萃取物、過濾且蒸發為殘餘物。藉由管柱層析以0、1%及2%甲醇/二氯甲烷溶離，繼而Kugelrohr蒸餾且自2：1之己烷/乙酸乙酯再結晶來純化殘餘物。如由GC-MS所證實獲得5g白色固體(56%產率)。 A mixture of 2-(3-methoxyphenyl)pyridine (9.7 g, 52.37 mmol) and pyridine hydrochloride (72.6 g, 628.44 mmol) was obtained. The mixture was heated to 220 °C. The reaction was carried out for 2 hours. Water was added to the cooled mixture and then extracted twice with dichloromethane. The organic extract was dried over MgSO.sub.4, filtered and evaporated. The residue was purified by column chromatography eluting with 0, 1% and 2% methanol/methylene chloride, followed by Kugelrohr distillation and recrystallization from 2:1 hexane/ethyl acetate. 5 g of a white solid (56% yield) was obtained as confirmed by GC-MS.
製備3-(吡啶-2-基)苯酚(5g，29.21mmol)於100mL二氯甲烷中之溶液。向該溶液中添加吡啶(4.7mL，58.42mmol)且在冰鹽浴中冷卻溶液。向該溶液中逐滴添加三氟甲烷磺酸酐(9.8mL，58.42mmol)於20mL二氯甲烷中之溶液。使反應緩慢加溫且在2小時後完成。添加水及二氯甲烷且分離各層。以二氯甲烷萃取含水層。經硫酸鎂乾燥有機層、過濾且蒸發至殘餘物。藉由管柱層析以5%、10%及15%乙酸乙酯/己烷溶離來純化殘餘物。如由GC-MS所證實獲得8g澄清液體(90%產率)。 A solution of 3-(pyridin-2-yl)phenol (5 g, 29.21 mmol) in 100 mL dichloromethane was obtained. Pyridine (4.7 mL, 58.42 mmol) was added to the solution and the solution was cooled in ice ice bath. A solution of trifluoromethanesulfonic anhydride (9.8 mL, 58.42 mmol) in 20 mL of dichloromethane was added dropwise to this solution. The reaction was allowed to warm slowly and was completed after 2 hours. Water and dichloromethane were added and the layers were separated. The aqueous layer was extracted with dichloromethane. The organic layer was dried over MgSO4, filtered and evaporatedEtOAc. The residue was purified by column chromatography eluting with 5%, 10% and 15% ethyl acetate/hexane. 8 g of clear liquid (90% yield) was obtained as confirmed by GC-MS.
在500ML圓形瓶燒瓶中混合3.85公克(2.41mmol)上述氯-橋接銥 二聚體、1.42公克(5.3mmol)三氟甲磺酸銀AgOSOCF3、2.93公克(9.64mmol)三氟甲烷磺酸3-(吡啶-2-基)苯酯及約300ml 2-乙氧基乙醇。在氮下將混合物加熱至回流，歷時24小時。在矽膠上以於己烷中之50%二氯甲烷純化反應混合物。自含有爭奪4個配位子之銥錯合物的反應混合物分離約900mg產物。由LC-MC證實產物。可經由管柱層析獲得所需溶離份。 3.85 g (2.41 mmol) of the above-mentioned chlorine-bridged ruthenium dimer, 1.42 g (5.3 mmol) of silver trifluoromethanesulfonate AgOSOCF 3 and 2.93 g (9.64 mmol) of trifluoromethanesulfonic acid 3 were mixed in a 500 ML round flask. -(pyridin-2-yl)phenyl ester and about 300 ml of 2-ethoxyethanol. The mixture was heated to reflux under nitrogen for 24 hours. The reaction mixture was purified on silica gel in 50% dichloromethane in hexanes. Approximately 900 mg of product was isolated from a reaction mixture containing a ruthenium complex competing for 4 ligands. The product was confirmed by LC-MC. The desired fraction can be obtained by column chromatography.
將700mg(0.647mmol)三氟甲磺酸銥錯合物、394mg(3.23mmol)苯基酸、60mg Pd2(dba)3(0.065mmol)、110mg(0.268mmol)S-Phos、840mg(3.65mmol)K3PO4.H2O及50ml無水甲苯饋入100ml三頸燒瓶中。將反應混合物以氮鼓泡30分鐘，接著在氮下加熱至回流，歷時20小時。於矽膠管柱上分離反應混合物。如由NMR及LC-MS所證實獲得610mg固體(99%產率)。 700 mg (0.647 mmol) of ruthenium triflate complex, 394 mg (3.23 mmol) of phenyl Acid, 60 mg of Pd 2 (dba) 3 (0.065 mmol), 110 mg (0.268 mmol) of S-Phos, 840 mg (3.65 mmol) of K 3 PO 4 .H 2 O and 50 ml of anhydrous toluene were fed into a 100 ml three-necked flask. The reaction mixture was bubbled with nitrogen for 30 min then heated to reflux under nitrogen for 20 h. The reaction mixture was separated on a cartridge column. 610 mg solid (99% yield) was obtained as confirmed by NMR and LC-MS.
與無分離增強官能基之化合物相比，分離增強官能基可改變化合物之極性、尺寸及/或溶解性。因此，具有不同數目之分離增強官能基之化合物的混合物可經充分區分使得其可使用層析(TLC)分離。 一般而言，混合物之化合物的較大差異使得可較易於分離且使用TLC至少0.05之Rf差異可使得實際上正相矽膠管柱層析分離化合物之混合物。 Separating the enhanced functional groups can alter the polarity, size, and/or solubility of the compound as compared to a compound that does not separate the enhanced functional groups. Thus, mixtures of compounds having different numbers of discrete enhanced functional groups can be sufficiently differentiated such that they can be separated using chromatography (TLC). In general, the large differences in the compounds of the mixture make it easier to separate and the Rf difference of at least 0.05 using TLC can be such that a mixture of compounds is actually separated by normal phase tantalum column chromatography.
本文中在約23℃下於正相矽膠板(Sorbent Technologies,2.5cm×7.5cm×200μm，具有UV254螢光指示劑)上以己烷、二氯甲烷、乙酸乙酯、甲苯及/或甲醇之混合物作為移動相溶劑進行TLC。移動相溶劑系統經選擇以使得化合物混合物中之主要組份的Rf在0.2-0.8之範圍內。舉例而言，可以極性增加之次序己烷：二氯甲烷2：1、1：1或1：2；或以極性增加之次序己烷：乙酸乙酯2：1、1：1或1：2；或以極性增加之次序己烷：二氯甲烷：乙酸乙酯2：2：1、1：1：1或1：2：2。 Here, at about 23 ° C on a normal phase silicone sheet (Sorbent Technologies, 2.5 cm × 7.5 cm × 200 μm, with UV254 fluorescent indicator) with hexane, dichloromethane, ethyl acetate, toluene and / or methanol The mixture was subjected to TLC as a mobile phase solvent. The mobile phase solvent system is selected such that the Rf of the major component of the compound mixture is in the range of from 0.2 to 0.8. For example, the order of increasing polarity may be hexane: dichloromethane 2:1, 1:1 or 1:2; or in order of increasing polarity: hexane: ethyl acetate 2:1, 1:1 or 1:2 Or hexane in the order of increasing polarity: dichloromethane: ethyl acetate 2:2:1, 1:1:1 or 1:2:2.
使用層析分離不同化合物取決於化合物如何強烈地吸附於固定相上且如何可將其藉由移動相(溶離劑)解吸附。與無分離增強官能基之金屬錯合物相比，金屬錯合物上之分離增強官能基係用以增加金屬錯合物於固定相上之吸附。舉例而言，於2：3之二氯甲烷：己烷溶劑中之Ir(Br-ppy)(ppy)2及Ir(Brppy)2(ppy)具有0.22及0.27之Rf。此Rf差異對於分離而言並不現實。然而，二氯甲烷溶劑中之Ir(頻哪醇根基酸酯-ppy)(ppy)2及Ir(頻哪醇根基酸酯-ppy)2(ppy)分別具有0.68及0.16之Rf。Rf之此較大差異使得管柱分離兩種化合物成為現實。 Separation of different compounds using chromatography depends on how strongly the compound adsorbs on the stationary phase and how it can be desorbed by the mobile phase (solvent). The separation-enhancing functional groups on the metal complex are used to increase the adsorption of the metal complex on the stationary phase as compared to the metal complex without the separation-enhancing functional group. For example, Ir(Br-ppy)(ppy) 2 and Ir(Brppy) 2 (ppy) in a 2:3 dichloromethane:hexane solvent have an Rf of 0.22 and 0.27. This Rf difference is not realistic for separation. However, Ir in the solvent of dichloromethane (pinacol Acid ester-ppy) (ppy) 2 and Ir (pinadol base) The ester-ppy) 2 (ppy) has an R f of 0.68 and 0.16, respectively. This large difference in R f makes it practical to separate the two compounds from the column.
在層析中，吸附強度為分析物與固定相之間相互作用的結果。含有第二及第三列諸如硼、氮、氧、矽、磷或硫之雜原子的官能基可用作分離增強官能基。與諸如氟、氯、溴及碘之鹵素相比，其可產生與固定相更強之相互作用。其可為諸如硼、氮、氧、矽、磷或硫之雜原子的鹼性或酸性性質更強之結果。通常，相互作用具附加性，意謂每個分子之分離增強官能基愈多，則吸附愈強。移動相沿移動相移動之方向解吸附且溶離分析物。在正相層析中，移動相溶劑極性愈大，則解吸附愈快。因此，重要的係藉由調整極性與非極性溶劑之比率來 調整移動相溶劑之極性以達成分析物之合理移動。舉例而言，若溶劑系統過於具有非極性，則化合物在TCL板上將幾乎不行進(例如Rf小於0.1)，且不可達成有意義之分離。另一方面，若溶劑系統過於具有極性，則化合物在TCL板將行進得過快(例如Rf高於0.9)，且不可達成有意義之分離。兩種情況均由對於特定分離增強劑衍生之金屬錯合物的溶劑系統之錯誤選擇而產生。因此，選擇移動相溶劑系統以使得化合物混合物之主要組份的Rf在0.2-0.8之範圍內。 In chromatography, the adsorption strength is the result of the interaction between the analyte and the stationary phase. A functional group containing a second and a third column of a hetero atom such as boron, nitrogen, oxygen, helium, phosphorus or sulfur can be used as the separation-enhancing functional group. It produces a stronger interaction with the stationary phase than halogens such as fluorine, chlorine, bromine and iodine. It can be the result of stronger basic or acidic nature of heteroatoms such as boron, nitrogen, oxygen, helium, phosphorus or sulfur. Generally, the interaction is additive, meaning that the more the separation of each molecule enhances the functional group, the stronger the adsorption. The mobile phase desorbs and dissolves the analyte in the direction of movement of the mobile phase. In normal phase chromatography, the greater the polarity of the mobile phase solvent, the faster the desorption. Therefore, it is important to adjust the polarity of the mobile phase solvent by adjusting the ratio of polar to non-polar solvent to achieve reasonable movement of the analyte. For example, if the solvent system is too non-polar, the compound will travel little on the TCL plate (eg, Rf is less than 0.1) and no meaningful separation can be achieved. On the other hand, if the solvent system is too polar, the compound will travel too fast in the TCL plate (e.g., Rf is above 0.9) and no meaningful separation can be achieved. Both cases arise from the erroneous selection of solvent systems for metal complexes derived from specific separation enhancers. Therefore, the mobile phase solvent system is selected such that the Rf of the major component of the compound mixture is in the range of 0.2-0.8.
由於分析物由溶離劑攜帶，因此其需可溶於溶離劑。通常藉由分離增強官能基來增加金屬錯合物之溶解性，此為分離增強官能基之另一優點。 Since the analyte is carried by the eliminator, it needs to be soluble in the eliminator. The solubility of the metal complex is generally increased by separating the reinforcing functional groups, which is another advantage of separating the reinforcing functional groups.
在某些實施例中，分離增強官能基可提供其他反應路徑。其可為可在偶合反應、去保護、縮合、醯化等中反應之官能基。在某些實施例中，較佳之分離增強官能基為含有硼、氮、氧、矽、磷或硫中之一或多者的官能基。更佳之分離增強官能基為B(OH)2、B(OR)2、NH2、NHR、OTf、OTs、COOH或SiMe3；其中R為C1-20烴基部分。 In certain embodiments, isolating the enhanced functional groups can provide additional reaction pathways. It may be a functional group which can be reacted in a coupling reaction, deprotection, condensation, deuteration or the like. In certain embodiments, preferred separation enhancing functional groups are functional groups containing one or more of boron, nitrogen, oxygen, helium, phosphorus or sulfur. More preferably, the separation enhancing functional group is B(OH) 2 , B(OR) 2 , NH 2 , NHR, OTf, OTs, COOH or SiMe 3 ; wherein R is a C 1-20 hydrocarbyl moiety.
裝置實例Device instance
實例18、實例19與比較實例2為使用真空熱蒸發製造之有機發光裝置。在預塗有120nm厚氧化銦錫(ITO)陽極之玻璃基板上製造裝置。陰極為1nm之LiF層，繼而為100nm鋁。製造後立即在氮(<1ppm H2O及O2)下以經環氧樹脂密封之玻璃蓋囊封所有裝置，且將吸濕劑併入各裝置內。 Example 18, Example 19 and Comparative Example 2 are organic light-emitting devices manufactured using vacuum thermal evaporation. A device was fabricated on a glass substrate precoated with a 120 nm thick indium tin oxide (ITO) anode. The cathode was a 1 nm LiF layer followed by 100 nm aluminum. Immediately after the production with epoxy resin to seal the cover glass encapsulated devices all under nitrogen (<1ppm H 2 O and O 2), and the moisture absorbent is incorporated in each device.
對於實例18之裝置而言，使用以下各物製造有機堆疊：作為電洞注入層(HIL)之厚度為30nm之Ir(3-Meppy)3；作為電洞傳輸層(HTL)之厚度為30nm之N4,N4'-二(萘-1-基)-N4,N4'-雙(4-乙烯基苯基)聯苯-4,4'-二胺(α-NPD)；作為發射層之厚度為30nm之摻雜有磷光發射體化合物I-B(10重量%)之4,4'-二(9H-咔唑-9-基)聯苯(CBP)；作為第一電子 傳輸層(ETL1)之厚度為5nm之2,3,6,7,10,11-六苯基苯幷菲(HPT)；及作為第二電子傳輸層(ETL2)之厚度為45nm之參(8-羥基喹啉)鋁(Alq3)。 For the device of Example 18, an organic stack was fabricated using the following: Ir(3-Meppy) 3 having a thickness of 30 nm as a hole injection layer (HIL); and having a thickness of 30 nm as a hole transport layer (HTL) N 4, N 4 '- di (naphthalene-1-yl) -N 4, N 4' - bis (4-vinylphenyl) biphenyl-4,4'-diamine (α-NPD); as an emitter a layer having a thickness of 30 nm doped with a phosphorescent emitter compound IB (10% by weight) of 4,4'-bis(9H-carbazol-9-yl)biphenyl (CBP); as the first electron transport layer (ETL1) a thickness of 5,2,3,6,7,10,11-hexaphenylphenanthrene (HPT); and a second electron transport layer (ETL2) having a thickness of 45 nm (8-hydroxyquinoline) ) Aluminum (Alq 3 ).
除使用化合物V作為磷光發射體代替化合物I-B以外，以類似於實例18的方式製造實例19。除Ir(5'-Phppy)3用於HIL中代替Ir(3-Meppy)3且使用Ir(5'-Phppy)3(9重量%)作為磷光發射體代替化合物I-B以外，以類似於實例18的方式製造比較實例2。 Example 19 was made in a similar manner to Example 18 except that Compound V was used as the phosphorescent emitter instead of Compound IB. In place of Ir (3-Meppy) except Ir (5'-Phppy) 3 and is used for the HIL 3 3 (9 wt%) Ir (5'-Phppy) was used as the phosphorescent emitter in place of Compound IB, in a manner similar Example 18 The way to manufacture Comparative Example 2.
如表5中所示，化合物I-B及V在具有高於55cd/A之發光效率(LE)、高於15%之外部量子效率(EQE)、小於72nm之半高全寬(FWHM)及x<0.330、y>0.620之CIE的裝置中良好充當磷光摻雜劑。又，與Ir(5'-Phppy)3之322℃相比，化合物I-B具有231℃之蒸發溫度。與Ir(5'-Phppy)3相比，化合物I-B之較低蒸發溫度導致相對清潔之蒸發(以較少蒸發殘餘物為特徵)。此可有利於此等裝置之商業生產。化合 物V亦具有較低之蒸發溫度(246℃)及清潔蒸發。低蒸發溫度可為與Ir(5'-Phppy)3相比化合物I-B及V之較低分子量的結果。此等結果證明雜片段金屬錯合物可具有由如上所述之不同配位子所賦予之理想特性。 As shown in Table 5, the compounds IB and V have a luminous efficiency (LE) higher than 55 cd/A, an external quantum efficiency (EQE) higher than 15%, a full width at half maximum (FWHM) of less than 72 nm, and x < 0.330. The device of CIE with y>0.620 acts well as a phosphorescent dopant. Further, the compound IB had an evaporation temperature of 231 ° C as compared with 322 ° C of Ir(5'-Phppy) 3 . The lower evaporation temperature of Compound IB resulted in relatively clean evaporation (characterized by less evaporation residue) compared to Ir(5'-Phppy) 3 . This can be advantageous for the commercial production of such devices. Compound V also had a lower evaporation temperature (246 ° C) and clean evaporation. The low evaporation temperature can be the result of lower molecular weights of the compounds IB and V compared to Ir(5'-Phppy) 3 . These results demonstrate that the heterozygous metal complex can have desirable properties imparted by different ligands as described above.
應瞭解本文中所描述之各種實施例僅以實例方式，且並不意欲限制本發明之範疇。舉例而言，在不偏離本發明之精神的情況下，本文中所描述之許多材料及結構可經其他材料及結構取代。應瞭解關於本發明研究為何並不意欲限制之各種理論。舉例而言，與電荷轉移相關之理論並不意欲限制。 It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention. It should be understood that the various theories of the invention are not intended to be limited. For example, the theory related to charge transfer is not intended to be limiting.
材料定義：Material definition:
顏料綠-2：化合物G1、G2、G3及G4以2：37：53：7比率之化合物。 Pigment Green-2: Compounds of compounds G1, G2, G3 and G4 in a ratio of 2:37:53:7.
如本文中所用，縮寫係指如下材料： As used herein, abbreviations refer to the following materials:
CBP：4,4'-N,N-二咔唑-聯苯 CBP: 4,4'-N,N-dicarbazole-biphenyl
m-MTDATA 4,4',4"-參(3-甲基苯基苯基胺基)三苯基胺 m-MTDATA 4,4',4"-parade (3-methylphenylphenylamino)triphenylamine
Alq3：參(8-羥基喹啉)鋁(III) Alq 3 : ginseng (8-hydroxyquinoline) aluminum (III)
Bphen：4,7-二苯基-1,10-啡啉 Bphen: 4,7-diphenyl-1,10-morpholine
n-BPhen：n-摻雜之BPhen(摻雜有鋰) n-BPhen: n-doped BPhen (doped with lithium)
F4-TCNQ：四氟-四氰基-喏二甲烷 F 4 -TCNQ: tetrafluoro-tetracyano-quinodimethane
p-MTDATA：p-摻雜之m-MTDATA(摻雜有F4-TCNQ) p-MTDATA: p-doped m-MTDATA (doped with F 4 -TCNQ)
Ir(ppy)3：參(2-苯基吡啶)-銥 Ir(ppy) 3 : ginseng (2-phenylpyridine)-oxime
Ir(ppz)3：參(1-苯基吡唑根基，N,C(2')銥(III) Ir(ppz) 3 : ginseng (1-phenylpyrazolyl, N, C(2') 铱(III)
BCP：2,9-二甲基-4,7-二苯基-1,10-啡啉 BCP: 2,9-dimethyl-4,7-diphenyl-1,10-morpholine
TAZ：3-苯基-4-(1'-萘基)-5-苯基-1,2,4-*** TAZ: 3-phenyl-4-(1'-naphthyl)-5-phenyl-1,2,4-triazole
CuPc：銅酞菁 CuPc: copper phthalocyanine
ITO：氧化銦錫 ITO: indium tin oxide
NPD：N,N'-二苯基-N-N'-二(1-萘基)-聯苯胺 NPD: N,N'-diphenyl-N-N'-bis(1-naphthyl)-benzidine
TPD：N,N'-二苯基-N-N'-二(3-甲苯基)-聯苯胺 TPD: N,N'-diphenyl-N-N'-bis(3-tolyl)-benzidine
BAlq：鋁(III)雙(2-甲基-8-羥基喹啉根基)4-苯基酚鹽 BAlq: aluminum (III) bis(2-methyl-8-hydroxyquinolinyl) 4-phenylphenolate
mCP：1,3-N,N-二咔唑-苯 mCP: 1,3-N,N-dicarbazole-benzene
DCM：4-(二氰基伸乙基)-6-(4-二甲基胺基苯乙烯基-2-甲基)-4H-哌喃 DCM: 4-(dicyanoethyl)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyran
DMQA：N,N'-二甲基喹吖啶酮 DMQA: N, N'-dimethyl quinacridone
PEDOT：PSS：聚(3,4-伸乙二氧基噻吩)與聚苯乙烯磺酸酯(PSS)之水性分散液 PEDOT: PSS: aqueous dispersion of poly(3,4-extended ethylenedioxythiophene) and polystyrene sulfonate (PSS)
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