TW201509920A - Compound, linght-emitting material and organic electroluminescence device - Google Patents
Compound, linght-emitting material and organic electroluminescence device Download PDFInfo
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- TW201509920A TW201509920A TW103118144A TW103118144A TW201509920A TW 201509920 A TW201509920 A TW 201509920A TW 103118144 A TW103118144 A TW 103118144A TW 103118144 A TW103118144 A TW 103118144A TW 201509920 A TW201509920 A TW 201509920A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 107
- 239000000463 material Substances 0.000 title claims abstract description 93
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- 239000002861 polymer material Substances 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000004882 thiopyrans Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
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Abstract
Description
本發明係關於一種可用作發光材料之化合物及使用其之有機發光元件。 The present invention relates to a compound which can be used as a light-emitting material and an organic light-emitting element using the same.
提高有機電致發光元件(有機EL(Electroluminescence，電致發光)元件)等有機發光元件之發光效率之研究正在盛行。尤其是進行有各種藉由新開發構成有機電致發光元件之電子傳輸材料、電洞傳輸材料、發光材料等並加以組合而提高發光效率的研究。其中，亦可見有關利用含有吩嗪結構之化合物之有機電致發光元件之研究，迄今為止亦已提出若干提案。 Research on improving the luminous efficiency of organic light-emitting elements such as organic electroluminescent elements (organic EL (Electroluminescence) elements) is prevailing. In particular, various studies have been conducted to improve the luminous efficiency by newly combining an electron transporting material, a hole transporting material, a light emitting material, and the like which constitute an organic electroluminescent element. Among them, it can also be seen that Studies on organic electroluminescent elements of phenazine-based compounds have so far been proposed.
例如，於專利文獻1中，記載有於存在於構成發光元件之一對電極間之有機層中，使用含有下述通式所表示之吩嗪結構之化合物。關於下述通式，規定R1及R2為經取代或未經取代之芳基，或經取代或未經取代之雜環基。 For example, Patent Document 1 describes that the organic layer existing between one of the pair of electrodes constituting the light-emitting element is represented by the following formula. a compound of the phenazine structure. With respect to the following formula, R 1 and R 2 are defined as a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
於專利文獻1中，記載有包含較廣範圍之結構作為R1及R2之通式，但僅記載8種具體之結構。於實施例中確認使用其中7種化合物之發光元件發光，其中，顯示使用具有下述結構之化合物之發光元件具有相對良好之亮度及耐久性。 Patent Document 1 describes a general formula including R 1 and R 2 in a wide range of structures, but only eight specific structures are described. In the examples, it was confirmed that light-emitting elements using seven kinds of compounds emit light, and among them, light-emitting elements using a compound having the following structure were shown to have relatively good brightness and durability.
[專利文獻1]日本專利特開2000-21574號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-21574
關於如此含有吩嗪結構等之化合物，此前正進行關於應用於有機電致發光元件之提案。然而，關於在與形成吩嗪骨架之氮原子鍵結之芳基進而鍵結有三環、苯并唑環、苯并噻唑環等之化合物，並未進行具體之研究。又，大部分具有此種結構之化合物甚至於合成例中亦未得到報告。因此，極其難以正確地預測具有該等結構之化合物顯示何種性質。又，專利文獻1中具體地顯示具有良好之亮度及耐久性之化合物就發光效率之方面而言有改善之餘地，但關於採用何種結構可改善發光效率之方面，專利文獻1中未有任何提示。 About this inclusion A compound such as a phenazine structure has been proposed for application to an organic electroluminescence device. However, regarding the formation and formation The aryl group bonded to the nitrogen atom of the phenazine skeleton is bonded to three Ring, benzo Compounds such as azole rings and benzothiazole rings have not been specifically studied. Also, most of the compounds having such a structure have not been reported even in the synthesis examples. Therefore, it is extremely difficult to correctly predict which properties of compounds having such structures are exhibited. Further, Patent Document 1 specifically shows that a compound having good brightness and durability has room for improvement in terms of luminous efficiency, but there is no patent document 1 in terms of which structure can be used to improve luminous efficiency. prompt.
本發明者等人考慮到該等先前技術之問題，以提供一種含有吩嗪結構且發光效率較高之化合物為目的進行研究。又，亦以導出可用作發光材料之化合物之通式，概括發光效率較高之有機發光元件之構 成為目的而進行努力研究。 The inventors of the present invention have considered the problems of the prior art to provide a A compound having a phenazine structure and a high luminous efficiency is studied for the purpose. In addition, efforts have been made for the purpose of deriving a general formula of a compound which can be used as a light-emitting material, and an organic light-emitting element having a high luminous efficiency.
本發明者等人為了達成上述目的而進行努力研究，結果成功地合成在與形成吩嗪骨架之氮原子鍵結之芳基進而鍵結有三環、苯并唑環、苯并噻唑環等之化合物，並且首次明確該等化合物可用作發光材料。又，發現於此種化合物中存在可用作延遲螢光材料者，明確可廉價地提供發光效率較高之有機發光元件。本發明者等人基於該等見解，提供以下之本發明作為解決上述問題之手段。 The present inventors conducted an effort to achieve the above object, and the results were successfully synthesized and formed. The aryl group bonded to the nitrogen atom of the phenazine skeleton is bonded to three Ring, benzo Compounds such as azole rings, benzothiazole rings, etc., and for the first time it is clear that such compounds can be used as luminescent materials. Further, it has been found that such a compound can be used as a delayed fluorescent material, and it is clear that an organic light-emitting element having high luminous efficiency can be provided at low cost. Based on these findings, the inventors of the present invention have provided the following invention as means for solving the above problems.
[1]一種由下述通式(1)所表示之化合物，通式(1)A-D-A [1] A compound represented by the following formula (1), a formula (1) A-D-A
[通式(1)中，D為包含下述式：
所表示之結構(其中，結構中之氫原子可經取代基取代)之二價基，2個A分別獨立表示選自下述群：
之結構(其中，結構中之氫原子可經取代基取代)之基]。 The structure of the structure in which a hydrogen atom in the structure may be substituted with a substituent].
[2]如[1]記載之化合物，其特徵在於：通式(1)之D具有下述通式(2)所表示之結構，[化5]
[通式(2)中，R1~R8分別獨立表示氫原子或取代基；R1與R2、R2與R3、R3與R4、R5與R6、R6與R7、R7與R8可相互鍵結而形成環狀結構]。 [In the formula (2), R 1 to R 8 each independently represent a hydrogen atom or a substituent; R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7. R 7 and R 8 may be bonded to each other to form a cyclic structure].
[3]如[1]或[2]記載之化合物，其特徵在於：通式(1)之2個A具有相同結構。 [3] The compound according to [1] or [2], wherein the two A's of the formula (1) have the same structure.
[4]如[1]至[3]中任一項記載之化合物，其特徵在於以下述通式(3)所表示，
[通式(3)中，R1~R8及R11~R20分別獨立表示氫原子或取代基； R1與R2、R2與R3、R3與R4、R5與R6、R6與R7、R7與R8、R11與R12、R12與R13、R13與R14、R14與R15、R16與R17、R17與R18、R18與R19、R19與R20可相互鍵結而形成環狀結構；其中，通式(3)滿足以下之<1>及<2>之條件； [In the formula (3), R 1 to R 8 and R 11 to R 20 each independently represent a hydrogen atom or a substituent; R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 16 and R 17 , R 17 and R 18 , R 18 and R 19 , R 19 and R 20 may be bonded to each other to form a cyclic structure; wherein, the general formula (3) satisfies the following conditions of <1> and <2>;
<1>R12為氰基或下述結構之基(其中，氫原子可經取代基取代)，或
R13為氰基或下述群中任一結構之基(其中，氫原子可經取代基取代)，或者
R12與R13為相互鍵結而與R12及R13所鍵結之苯環共同形成下述任
一結構之基(其中，氫原子可經取代基取代)；
<2>R17為氰基或下述結構之基(其中，氫原子可經取代基取代)，或
R18為氰基或下述群中任一結構之基(其中，氫原子可經取代基取代)，或者
R17與R18為相互鍵結而與R17及R18所鍵結之苯環共同形成下述任一結構之基(其中，氫原子可經取代基取代) R 17 and R 18 are mutually bonded to form a group of any of the following structures together with a benzene ring to which R 17 and R 18 are bonded (wherein a hydrogen atom may be substituted with a substituent)
[5]如[4]記載之化合物，其特徵在於：通式(3)之R1~R8分別獨立為氫原子、碳數1~10之經取代或未經取代之烷基、碳數1~10之經取代或未經取代之烷氧基、碳數6~15之經取代或未經取代之芳基、或者碳數3~12之經取代或未經取代之雜芳基。 [5] The compound according to [4], wherein R 1 to R 8 in the formula (3) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a carbon number; a substituted or unsubstituted alkoxy group of 1 to 10, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
[6]如[4]或[5]記載之化合物，其特徵在於：以通式(3)之R12、R13、R17、R18中之至少兩者滿足上述<1>及<2>之條件之方式具有取代基，其等以外之R11~R20分別獨立為氫原子、氟原子、氯原子、 氰基、碳數1~10之經取代或未經取代之烷基、碳數1~10之經取代或未經取代之烷氧基、碳數1~10之經取代或未經取代之二烷基胺基、碳數12~40之經取代或未經取代之二芳基胺基、碳數6~15之經取代或未經取代之芳基、或者碳數3~12之經取代或未經取代之雜芳基。 [6] The compound according to [4] or [5], wherein at least two of R 12 , R 13 , R 17 and R 18 of the formula (3) satisfy the above <1> and <2 The condition of the condition has a substituent, and the other R 11 to R 20 are independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and carbon. a substituted or unsubstituted alkoxy group of 1 to 10, a substituted or unsubstituted dialkylamino group having 1 to 10 carbon atoms, a substituted or unsubstituted diaryl group having 12 to 40 carbon atoms; a aryl group, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
[7]如[4]至[6]中任一項記載之化合物，其特徵在於：可取代通式(3)之上述<1>及<2>中所記載之結構之氫原子的取代基選自由氟原子、氯原子、氰基、碳數1~10之經取代或未經取代之烷基、碳數1~10之經取代或未經取代之烷氧基、碳數1~10之經取代或未經取代之二烷基胺基、碳數12~40之經取代或未經取代之二芳基胺基、碳數6~15之經取代或未經取代之芳基、及碳數3~12之經取代或未經取代之雜芳基所組成之群。 The compound of any one of the above-mentioned <1> and <2> of the above-mentioned <1> and <2> of the formula (3), which is a compound of the above-mentioned <1> and <2>. Selecting a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a carbon number of 1 to 10 a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted diarylamino group having 12 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, and carbon A group of substituted or unsubstituted heteroaryl groups of 3 to 12.
[8]一種發光材料，其包含如[1]至[7]中任一項記載之化合物。 [8] A luminescent material comprising the compound according to any one of [1] to [7].
[9]一種延遲螢光體，其具有上述通式(1)所表示之結構。 [9] A delayed phosphor having a structure represented by the above formula (1).
[10]一種有機發光元件，其特徵在於：其在基板上包括包含如[8]記載之發光材料之發光層。 [10] An organic light-emitting device comprising a light-emitting layer comprising the light-emitting material according to [8] on a substrate.
[11]如[10]記載之有機發光元件，其特徵在於放射延遲螢光。 [11] The organic light-emitting device according to [10], which is characterized in that the radiation is delayed in fluorescence.
[12]如[10]或[11]記載之有機發光元件，其特徵在於：其係有機電致發光元件。 [12] The organic light-emitting device according to [10] or [11], wherein the organic light-emitting device is an organic electroluminescence device.
本發明之化合物可用作發光材料。又，於本發明之化合物中包括放射延遲螢光者。將本發明之化合物用作發光材料之有機發光元件可實現較高之發光效率。 The compounds of the invention are useful as luminescent materials. Further, those having a delayed radiation fluorescence are included in the compound of the present invention. The organic light-emitting element using the compound of the present invention as a light-emitting material can achieve higher luminous efficiency.
1‧‧‧基板 1‧‧‧Substrate
2‧‧‧陽極 2‧‧‧Anode
3‧‧‧電洞注入層 3‧‧‧ hole injection layer
4‧‧‧電洞傳輸層 4‧‧‧ hole transport layer
5‧‧‧發光層 5‧‧‧Lighting layer
6‧‧‧電子傳輸層 6‧‧‧Electronic transport layer
7‧‧‧陰極 7‧‧‧ cathode
圖1係表示有機電致發光元件之層構成例之概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing an example of a layer configuration of an organic electroluminescence device.
圖2係實施例2之使用化合物1之薄膜型有機光致發光元件之暫態衰減曲線。 Figure 2 is a graph showing the transient decay curve of the film type organic photoluminescent device of Example 2 using Example 1.
圖3係實施例2之使用化合物2之薄膜型有機光致發光元件之暫態衰減曲線。 Figure 3 is a graph showing the transient decay curve of the film type organic photoluminescent device of Example 2 using Compound 2.
圖4係實施例2之使用化合物5之薄膜型有機光致發光元件之暫態衰減曲線。 Figure 4 is a graph showing the transient decay curve of the film type organic photoluminescent device of Example 2 using Compound 5.
圖5係實施例2之使用化合物6之薄膜型有機光致發光元件之暫態衰減曲線。 Figure 5 is a graph showing the transient decay curve of the film type organic photoluminescent device of Example 2 using Compound 6.
圖6係實施例3之使用化合物1之有機電致發光元件之發光光譜。 Fig. 6 is an luminescence spectrum of the organic electroluminescence device using Compound 1 of Example 3.
圖7係表示實施例3之使用化合物1之有機電致發光元件之電流密度-電壓特性之圖表。 Fig. 7 is a graph showing the current density-voltage characteristics of the organic electroluminescent device using Compound 1 of Example 3.
圖8係實施例3之使用化合物2之有機電致發光元件之發光光譜。 Fig. 8 is an luminescence spectrum of the organic electroluminescence device using the compound 2 of Example 3.
圖9係表示實施例3之使用化合物2之有機電致發光元件之電流密度-電壓特性之圖表。 Fig. 9 is a graph showing current density-voltage characteristics of the organic electroluminescent device using Compound 2 of Example 3.
圖10係表示實施例3之使用化合物2之有機電致發光元件之亮度-外部量子效率特性之圖表。 Fig. 10 is a graph showing the luminance-external quantum efficiency characteristics of the organic electroluminescent device using Compound 2 of Example 3.
圖11係表示實施例3之使用化合物2之有機電致發光元件之電流密度-外部量子效率特性之圖表。 Fig. 11 is a graph showing the current density-external quantum efficiency characteristics of the organic electroluminescent device using Compound 2 of Example 3.
圖12係表示實施例3之使用化合物6之有機電致發光元件之電流密度-外部量子效率特性之圖表。 Fig. 12 is a graph showing the current density-external quantum efficiency characteristics of the organic electroluminescence device using Compound 6 of Example 3.
圖13係實施例3之使用化合物6之有機電致發光元件之發光光譜。 Figure 13 is an luminescence spectrum of an organic electroluminescence device using Compound 6 of Example 3.
圖14係表示實施例3之使用化合物6之有機電致發光元件之電流密度-電壓特性之圖表。 Fig. 14 is a graph showing the current density-voltage characteristics of the organic electroluminescent device using Compound 6 of Example 3.
圖15係表示實施例3之使用化合物6之有機電致發光元件之電流密度-外部量子效率特性之圖表。 Fig. 15 is a graph showing the current density-external quantum efficiency characteristics of the organic electroluminescence device using Compound 6 of Example 3.
以下，對本發明之內容詳細進行說明。以下所記載之構成必要 條件之說明有時係基於本發明之代表性實施態樣或具體例而進行，但本發明並不限定於此種實施態樣或具體例。再者，本說明書中使用「~」表示之數值範圍意指包含「~」之前後所記載之數值作為下限值及上限值之範圍。又，本發明所使用之化合物之分子內存在之氫原子之同位素種類並無特別限定，例如，分子內之氫原子可全部為1H，亦可一部分或全部為2H(氘D)。 Hereinafter, the contents of the present invention will be described in detail. The description of the constitutional requirements described below may be made based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples. In addition, the numerical range represented by "~" in this specification means the range which contains the numerical value of the [~~. Further, the isotopic type of the hydrogen atom present in the molecule of the compound used in the present invention is not particularly limited. For example, the hydrogen atoms in the molecule may be all 1 H, and some or all of them may be 2 H (氘D).
[通式(1)所表示之化合物] [Compound represented by the formula (1)]
本發明之化合物之特徵在於具有下述通式(1)所表示之結構。 The compound of the present invention is characterized by having a structure represented by the following formula (1).
通式(1)A-D-A General formula (1) A-D-A
通式(1)中，D表示包含下述式所表示之結構之二價基。 In the formula (1), D represents a divalent group containing a structure represented by the following formula.
上述結構中所存在之氫原子可經取代基取代。取代基之數並無特別限制，亦可不存在取代基。又，於存在2個以上之取代基時，該等取代基相互可相同，亦可不同。 The hydrogen atom present in the above structure may be substituted with a substituent. The number of substituents is not particularly limited, and a substituent may not be present. Further, when two or more substituents are present, the substituents may be the same or different from each other.
作為取代基，例如可列舉：羥基、鹵素原子、碳數1~20之烷基、碳數1~20之烷氧基、碳數1~20之烷硫基、碳數6~40之芳基、碳數3~40之雜芳基、碳數2~10之烯基、碳數2~10之炔基、碳數1~10之鹵烷基、碳數3~20之三烷基矽烷基、碳數4~20之三烷基矽烷基烷基、碳數5~20之三烷基矽烷基烯基、碳數5~20之三烷基矽烷基炔 基等。該等具體例之中，可進一步經取代基取代者亦可經取代。更佳之取代基為碳數1~20之經取代或未經取代之烷基、碳數1~20之烷氧基、碳數6~40之經取代或未經取代之芳基、碳數3~40之經取代或未經取代之雜芳基。進而較佳之取代基為碳數1~10之經取代或未經取代之烷基、碳數1~10之經取代或未經取代之烷氧基、碳數6~15之經取代或未經取代之芳基、碳數3~12之經取代或未經取代之雜芳基。 Examples of the substituent include a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an aryl group having 6 to 40 carbon atoms. , a heteroaryl group having 3 to 40 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, and a trialkylalkyl group having 3 to 20 carbon atoms. a trialkylsulfanylalkyl group having 4 to 20 carbon atoms, a trialkyldecylalkylene group having 5 to 20 carbon atoms, and a trialkyldecylalkylene group having 5 to 20 carbon atoms Base. Among these specific examples, those which may be further substituted by a substituent may be substituted. More preferred substituents are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, and carbon number 3 ~40 substituted or unsubstituted heteroaryl. Further preferably, the substituent is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon number of 6 to 15. Substituted aryl, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms.
烷基可為直鏈狀、支鏈狀、環狀之任一種，更佳為碳數1~6，作為具體例，可列舉：甲基、乙基、丙基、丁基、第三丁基、戊基、己基、異丙基。烷氧基可為直鏈狀、支鏈狀、環狀之任一種，更佳為碳數1~6，作為具體例，可列舉：甲氧基、乙氧基、丙氧基、丁氧基、第三丁氧基、戊氧基、己氧基、異丙氧基。可用作取代基之芳基可為單環，亦可為縮合環，作為具體例，可列舉苯基、萘基。雜芳基亦是可為單環，亦可為縮合環，作為具體例，可列舉吡啶基、嗒基、嘧啶基、三基、***基、苯并***基。該等雜芳基可為經由雜原子而鍵結之基，亦可為經由構成雜芳基環之碳原子而鍵結之基。 The alkyl group may be any of a linear chain, a branched chain, and a cyclic group, and more preferably has a carbon number of 1 to 6. As a specific example, a methyl group, an ethyl group, a propyl group, a butyl group, and a t-butyl group may be mentioned. , pentyl, hexyl, isopropyl. The alkoxy group may be any of a linear chain, a branched chain, and a cyclic group, and more preferably has a carbon number of 1 to 6, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. , a third butoxy group, a pentyloxy group, a hexyloxy group, an isopropoxy group. The aryl group which can be used as a substituent may be a single ring or a condensed ring, and specific examples thereof include a phenyl group and a naphthyl group. The heteroaryl group may be a single ring or a condensed ring, and specific examples thereof include a pyridyl group and a fluorene group. Base, pyrimidinyl, three Base, triazolyl, benzotriazolyl. The heteroaryl group may be a group bonded via a hetero atom or a group bonded via a carbon atom constituting the heteroaryl ring.
較佳為通式(1)之D為具有下述通式(2)所表示之結構之基。 D of the formula (1) is preferably a group having a structure represented by the following formula (2).
通式(2)中，R1~R8分別獨立表示氫原子或取代基。R1~R8亦可全部為氫原子。又，於2個以上為取代基之情形時，該等取代基可相同，亦可不同。關於R1~R8可取之取代基之說明及較佳範圍，可參照上述通式(1)之D可取之取代基之說明及較佳範圍。 In the formula (2), R 1 to R 8 each independently represent a hydrogen atom or a substituent. R 1 to R 8 may all be a hydrogen atom. Further, when two or more substituents are used, the substituents may be the same or different. For the description and preferred ranges of the substituents which may be taken from R 1 to R 8 , reference may be made to the description of the substituents of the above formula (1) and the preferred ranges.
R1與R2、R2與R3、R3與R4、R5與R6、R6與R7、R7與R8可相互鍵結而形成環狀結構。環狀結構可為芳香環，亦可為脂肪環，又，可為包含雜原子者，進而，環狀結構亦可為2環以上之縮合環。作為此處所謂之雜原子，較佳為選自由氮原子、氧原子及硫原子所組成之群中者。作為所形成之環狀結構之例，可列舉：苯環、萘環、吡啶環、嗒環、嘧啶環、吡環、吡咯環、咪唑環、吡唑環、***環、咪唑啉環、唑環、異唑環、噻唑環、異噻唑環、環己二烯環、環己烯環、環戊烯環、環庚三烯環、環庚二烯環、環庚烯環等。 R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , and R 7 and R 8 may be bonded to each other to form a cyclic structure. The cyclic structure may be an aromatic ring, an aliphatic ring, or a hetero atom. Further, the cyclic structure may be a condensed ring of two or more rings. The hetero atom referred to herein is preferably selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Examples of the cyclic structure to be formed include a benzene ring, a naphthalene ring, a pyridine ring, and an anthracene. Ring, pyrimidine ring, pyridyl Ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, imidazoline ring, Oxazole ring, different An azole ring, a thiazole ring, an isothiazole ring, a cyclohexadiene ring, a cyclohexene ring, a cyclopentene ring, a cycloheptatriene ring, a cycloheptadiene ring, a cycloheptene ring or the like.
作為通式(2)所表示之結構之較佳例，可列舉R1~R8全部為氫原子之結構。又，亦可列舉R1與R8、R2與R7、R3與R6、R4與R5分別相同之線對稱之結構，或R1與R5、R2與R6、R3與R7、R4與R8分別相同之旋轉對稱之結構。 Preferred examples of the structure represented by the formula (2) include those in which all of R 1 to R 8 are hydrogen atoms. Further, a structure in which R 1 and R 8 , R 2 and R 7 , R 3 and R 6 , R 4 and R 5 are respectively identical in line symmetry, or R 1 and R 5 , R 2 and R 6 , R may be mentioned. 3 is the same rotationally symmetric structure as R 7 , R 4 and R 8 respectively.
通式(1)中，A表示選自下述群之結構之基。 In the formula (1), A represents a group selected from the group consisting of the following groups.
上述群中所記載之結構中所存在之各氫原子可經取代基取代。取代基之數並無特別限制，亦可不存在取代基。又，於存在2個以上之取代基時，該等取代基相互可相同，亦可不同。 Each of the hydrogen atoms present in the structure described in the above group may be substituted with a substituent. The number of substituents is not particularly limited, and a substituent may not be present. Further, when two or more substituents are present, the substituents may be the same or different from each other.
作為可取代上述群中所記載之結構中所存在之氫原子的取代 基，例如可列舉：羥基、鹵素原子、氰基、碳數1~20之烷基、碳數1~20之烷氧基、碳數1~20之烷硫基、碳數1~20之烷基取代胺基、碳數12~40之芳基取代胺基、碳數2~20之醯基、碳數6~40之芳基、碳數3~40之雜芳基、碳數12~40之經取代或未經取代之咔唑基、碳數2~10之烯基、碳數2~10之炔基、碳數2~10之烷氧基羰基、碳數1~10之烷基磺醯基、碳數1~10之鹵烷基、醯胺基、碳數2~10之烷基醯胺基、碳數3~20之三烷基矽烷基、碳數4~20之三烷基矽烷基烷基、碳數5~20之三烷基矽烷基烯基、碳數5~20之三烷基矽烷基炔基及硝基等。該等具體例之中，可進一步經取代基取代者亦可經取代。更佳之取代基為鹵素原子、氰基、碳數1~20之經取代或未經取代之烷基、碳數1~20之烷氧基、碳數6~40之經取代或未經取代之芳基、碳數3~40之經取代或未經取代之雜芳基、碳數1~10之經取代或未經取代之二烷基胺基、碳數12~40之經取代或未經取代之二芳基胺基、碳數12~40之經取代或未經取代之咔唑基。進而較佳之取代基為氟原子、氯原子、氰基、碳數1~10之經取代或未經取代之烷基、碳數1~10之經取代或未經取代之烷氧基、碳數1~10之經取代或未經取代之二烷基胺基、碳數12~40之經取代或未經取代之二芳基胺基、碳數6~15之經取代或未經取代之芳基、碳數3~12之經取代或未經取代之雜芳基。 As a substitute for a hydrogen atom which may be substituted in the structure described in the above group Examples of the group include a hydroxyl group, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. Substituted amine group, aryl substituted amine group having 12 to 40 carbon atoms, fluorenyl group having 2 to 20 carbon atoms, aryl group having 6 to 40 carbon atoms, heteroaryl group having 3 to 40 carbon atoms, carbon number 12 to 40 Substituted or unsubstituted carbazolyl, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, alkylsulfonyl having 1 to 10 carbon atoms Sulfhydryl group, haloalkyl group having 1 to 10 carbon atoms, decylamino group, alkyl guanamine group having 2 to 10 carbon atoms, trialkylsulfonyl group having 3 to 20 carbon atoms, and trialkyl group having 4 to 20 carbon atoms a mercaptoalkyl group, a trialkylsulfonylalkenyl group having 5 to 20 carbon atoms, a trialkylsulfanylalkynyl group having 5 to 20 carbon atoms, and a nitro group. Among these specific examples, those which may be further substituted by a substituent may be substituted. More preferred substituents are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon number of 6 to 40. An aryl group, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted dialkylamino group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon number of 12 to 40 Substituted diarylamine group, substituted or unsubstituted carbazolyl group having 12 to 40 carbon atoms. Further preferred substituents are a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a carbon number. a substituted or unsubstituted dialkylamino group of 1 to 10, a substituted or unsubstituted diarylamino group having 12 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
對上述群中所記載之結構中所存在之相鄰之環骨架原子所鍵結之氫原子彼此，亦可使取代基相互鍵結而形成環狀結構。環狀結構可為芳香環，亦可為脂肪環，又，可為包含雜原子者，進而，環狀結構亦可為2環以上之縮合環。關於具體例，可參照上述通式(2)之環狀結構之具體例。 The hydrogen atoms bonded to the adjacent ring skeleton atoms existing in the structure described in the above group may be bonded to each other to form a cyclic structure. The cyclic structure may be an aromatic ring, an aliphatic ring, or a hetero atom. Further, the cyclic structure may be a condensed ring of two or more rings. For a specific example, a specific example of the cyclic structure of the above formula (2) can be referred to.
上述群中所記載之結構中較佳為
中之任一結構，進而較佳為
中之任一結構。 Any of the structures.
通式(1)之2個A相互可相同，亦可不同，較佳為相同。於2個A相互相同時，較佳為分子整體成為線對稱或點對稱。 The two A's of the formula (1) may be the same or different, and are preferably the same. When two A's are identical to each other, it is preferred that the entire molecule be line-symmetric or point-symmetric.
通常之發光材料具有發揮作為受體之作用之A及發揮作為施體之作用之D鍵結而成之A-D結構。與此相對，通式(1)所表示之化合物具有A-D-A之結構，於發揮作為施體之作用之D鍵結有2個發揮作為受體之作用之A。若鍵結有2個以上之A，則通常擔心作為受體之功能相互消除，產生分子未有效地發揮作為發光材料之功能之危險性。然而，已明瞭：藉由根據本發明，分別精選AD並相互組合，可提供發光效率較高、具有優異效果之發光材料。認為其原因在於：以分子等級控制HOMO(Highest Occupied Molecular Orbital，最高佔有分子軌道)及LUMO(Lowest Unoccupied Molecular Orbital，最低未占分子軌道)之擴散，使其滿足適合作為發光材料之條件。 A general luminescent material has an A-D structure which functions as an acceptor and a D-bond which functions as a donor. On the other hand, the compound represented by the formula (1) has a structure of A-D-A, and the D bond which functions as a donor has two functions which function as a receptor. When two or more As are bonded, it is generally feared that the functions as receptors are mutually eliminated, and there is a risk that molecules will not function effectively as a light-emitting material. However, it has been clarified that by separately selecting AD and combining them according to the present invention, it is possible to provide a luminescent material having high luminous efficiency and excellent effects. The reason is considered to be that the diffusion of HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) is controlled at a molecular level to satisfy a condition suitable as a luminescent material.
較佳為通式(1)所表示之化合物為具有下述通式(3)所表示之結構之化合物。 The compound represented by the formula (1) is preferably a compound having a structure represented by the following formula (3).
通式(3)中，R1~R8及R11~R20分別獨立表示氫原子或取代基。R1與R2、R2與R3、R3與R4、R5與R6、R6與R7、R7與R8、R11與R12、R12與R13、R13與R14、R14與R15、R16與R17、R17與R18、R18與R19、R19與R20 可相互鍵結而形成環狀結構。關於R1~R8可取之取代基之說明及較佳範圍，可參照通式(1)對應之記載。關於R11~R20可取之取代基之說明及較佳範圍，可參照可存在於通式(1)之A之取代基之記載。再者，通式(3)滿足以下之<1>及<2>之條件。 In the formula (3), R 1 to R 8 and R 11 to R 20 each independently represent a hydrogen atom or a substituent. R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 11 and R 12 , R 12 and R 13 , R 13 And R 14 , R 14 and R 15 , R 16 and R 17 , R 17 and R 18 , R 18 and R 19 , R 19 and R 20 may be bonded to each other to form a cyclic structure. The description and preferred ranges of the substituents which may be taken from R 1 to R 8 can be referred to the corresponding description of the formula (1). For the description and preferred ranges of the substituents which may be used for R 11 to R 20 , reference may be made to the description of the substituent which may be present in A of the formula (1). Further, the general formula (3) satisfies the conditions of <1> and <2> below.
<1>R12為氰基或下述結構之基(其中，氫原子可經取代基取代)，或
R13為氰基或下述群中任一結構之基(其中，氫原子可經取代基取代)，或者
R12與R13為相互鍵結而與R12及R13所鍵結之苯環共同形成下述任 一結構之基(其中，氫原子可經取代基取代)。 R 12 and R 13 are a group bonded to each other and to a benzene ring to which R 12 and R 13 are bonded to form a structure of any of the following structures (wherein a hydrogen atom may be substituted with a substituent).
<2>R17為氰基或下述結構之基(其中，氫原子可經取代基取代)，或
R18為氰基或下述群中任一結構之基(其中，氫原子可經取代基取代)，或者
R17與R18為相互鍵結而與R17及R18所鍵結之苯環共同形成下述任一結構之基(其中，氫原子可經取代基取代)。 R 17 and R 18 are a group bonded to each other and to a benzene ring to which R 17 and R 18 are bonded to form a structure of any one of the following structures (wherein a hydrogen atom may be substituted with a substituent).
關於上述<1>及<2>中所記載之結構之說明，可參照通式(1)之A之結構對應之記載。 For the description of the structures described in <1> and <2> above, the description of the structure corresponding to A of the general formula (1) can be referred to.
較佳為通式(3)之R1~R8分別獨立為氫原子、碳數1~10之經取代或未經取代之烷基、碳數1~10之經取代或未經取代之烷氧基、碳數6~15之經取代或未經取代之芳基、碳數3~12之經取代或未經取代之雜芳基。 Preferably, R 1 to R 8 of the formula (3) are independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. An oxy group, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
又，較佳為以通式(3)之R12、R13、R17、R18中之至少兩者滿足上 述<1>及<2>之條件之方式具有取代基，其等以外之R11~R18分別獨立為氫原子、氟原子、氯原子、氰基、碳數1~10之經取代或未經取代之烷基、碳數1~10之經取代或未經取代之烷氧基、碳數1~10之經取代或未經取代之二烷基胺基、碳數12~40之經取代或未經取代之二芳基胺基、碳數6~15之經取代或未經取代之芳基、或碳數3~12之經取代或未經取代之雜芳基。 Further, it is preferable that at least two of R 12 , R 13 , R 17 and R 18 of the formula (3) satisfy the conditions of the above <1> and <2>, and have a substituent other than R 11 to R 18 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. a substituted or unsubstituted dialkylamino group having 1 to 10 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 40 carbon atoms, or a substituted or unsubstituted carbon number of 6 to 15 a substituted aryl group or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
進而，較佳為可取代通式(3)之上述<1>及<2>中所記載之結構之氫原子的取代基選自由氟原子、氯原子、氰基、碳數1~10之經取代或未經取代之烷基、碳數1~10之經取代或未經取代之烷氧基、碳數1~10之經取代或未經取代之二烷基胺基、碳數12~40之經取代或未經取代之二芳基胺基、碳數6~15之經取代或未經取代之芳基、及碳數3~12之經取代或未經取代之雜芳基所組成之群。 Furthermore, it is preferable that the substituent of the hydrogen atom of the structure described in the above <1> and <2> of the formula (3) is selected from a fluorine atom, a chlorine atom, a cyano group, and a carbon number of 1 to 10. Substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, substituted or unsubstituted dialkylamino group having 1 to 10 carbon atoms, carbon number 12 to 40 a substituted or unsubstituted diarylamine group, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms; group.
以下，例示通式(1)所表示之化合物之具體例。然而，本發明中可使用之通式(1)所表示之化合物並不應受該等具體例之限定性解釋。 Specific examples of the compound represented by the formula (1) are exemplified below. However, the compound represented by the formula (1) which can be used in the present invention is not to be construed as being limited by the specific examples.
關於通式(1)所表示之化合物之分子量，例如於意欲藉由蒸鍍法將包含通式(1)所表示之化合物之有機層製膜並加以利用之情形時， 較佳為1500以下，更佳為1200以下，進而較佳為1000以下，進而更佳為800以下。分子量之下限值為通式(1)所表示之最小化合物之分子量。 The molecular weight of the compound represented by the formula (1) is, for example, a case where an organic layer containing the compound represented by the formula (1) is formed by a vapor deposition method and used. It is preferably 1,500 or less, more preferably 1200 or less, further preferably 1,000 or less, and still more preferably 800 or less. The lower limit of the molecular weight is the molecular weight of the smallest compound represented by the formula (1).
通式(1)所表示之化合物亦可不論分子量而藉由塗佈法成膜。若使用塗佈法，則即便為分子量相對較大之化合物，亦可成膜。 The compound represented by the formula (1) can also be formed into a film by a coating method regardless of the molecular weight. When a coating method is used, a film can be formed even if it is a compound having a relatively large molecular weight.
亦可想到應用本發明，將分子內含有複數個通式(1)所表示之結構之化合物用作發光材料。 It is also conceivable to apply the present invention to use a compound containing a plurality of structures represented by the formula (1) in a molecule as a light-emitting material.
例如，可想到使聚合性基預先存在於通式(1)所表示之結構中，並使該聚合性基進行聚合，將藉此所獲得聚合物用作發光材料。具體而言，可想到準備通式(1)之A或D之任一者中包含聚合性官能基之單體，使其進行均聚，或與其他單體一起進行共聚，藉此，獲得具有重複單元之聚合物，將該聚合物用作發光材料。或者，亦可想到藉由使具有通式(1)所表示之結構之化合物彼此反應而獲得二聚物或三聚物，將該等用作發光材料。 For example, it is conceivable that a polymerizable group is preliminarily present in the structure represented by the formula (1), and the polymerizable group is polymerized, and the polymer obtained thereby is used as a light-emitting material. Specifically, it is conceivable to prepare a monomer containing a polymerizable functional group in any one of A or D of the general formula (1), to homopolymerize it, or to copolymerize with another monomer, thereby obtaining The polymer of the repeating unit is used as a luminescent material. Alternatively, it is also conceivable to obtain a dimer or a trimer by reacting a compound having a structure represented by the general formula (1) with each other, and use these as a light-emitting material.
作為具有包含通式(1)所表示之結構之重複單元之聚合物之例，可列舉包含下述通式(4)或(5)所表示之結構之聚合物。 Examples of the polymer having a repeating unit having a structure represented by the formula (1) include a polymer having a structure represented by the following formula (4) or (5).
通式(4)及(5)中，Q表示含有通式(1)所表示之結構之基，L1及L2表示連結基。連結基之碳數較佳為0~20，更佳為1~15，進而較佳為 2~10。連結基較佳為具有-X11-L11-所表示之結構者。此處，X11表示氧原子或硫原子，較佳為氧原子。L11表示連結基，較佳為經取代或未經取代之伸烷基、或者經取代或未經取代之伸芳基，更佳為碳數1~10之經取代或未經取代之伸烷基、或者經取代或未經取代之伸苯基。 In the general formulae (4) and (5), Q represents a group containing a structure represented by the formula (1), and L 1 and L 2 represent a linking group. The carbon number of the linking group is preferably from 0 to 20, more preferably from 1 to 15, and still more preferably from 2 to 10. The linking group is preferably a structure represented by -X 11 -L 11 -. Here, X 11 represents an oxygen atom or a sulfur atom, preferably an oxygen atom. L 11 represents a linking group, preferably a substituted or unsubstituted alkylene group, or a substituted or unsubstituted extended aryl group, more preferably a substituted or unsubstituted alkylene group having a carbon number of 1 to 10. A phenyl group, either substituted or unsubstituted.
通式(4)及(5)中，R101、R102、R103及R104分別獨立表示取代基。較佳為碳數1~6之經取代或未經取代之烷基、碳數1~6之經取代或未經取代之烷氧基、鹵素原子，更佳為碳數1~3之未經取代之烷基、碳數1~3之未經取代之烷氧基、氟原子、氯原子，進而較佳為碳數1~3之未經取代之烷基、碳數1~3之未經取代之烷氧基。 In the general formulae (4) and (5), R 101 , R 102 , R 103 and R 104 each independently represent a substituent. Preferably, it is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a halogen atom, more preferably a carbon number of 1 to 3 Substituted alkyl group, unsubstituted alkoxy group having 1 to 3 carbon atoms, fluorine atom, chlorine atom, further preferably unsubstituted alkyl group having 1 to 3 carbon atoms, and having 1 to 3 carbon atoms Substituted alkoxy.
L1及L2所表示之連結基可鍵結於構成Q之通式(1)之結構之A或D、通式(3)之結構之R1~R8、R11~R18中之任一者。亦可於1個Q連結2個以上之連結基而形成交聯結構或網狀結構。 The linking group represented by L 1 and L 2 may be bonded to R 1 to R 8 and R 11 to R 18 of the structure of the formula (1) which constitutes the formula (1) of Q and R 1 to R 8 and R 11 to R 18 of the structure of the formula (3). Either. A crosslinked structure or a network structure may be formed by connecting two or more linking groups to one Q.
作為重複單元之具體之結構例，可列舉下述式(6)~(9)所表示之結構。 Specific examples of the configuration of the repeating unit include the structures represented by the following formulas (6) to (9).
具有包含該等式(6)~(9)之重複單元之聚合物可藉由以下方式合成：預先將羥基導入通式(1)之結構之A或D之任一者，將其作為連結子使下述化合物反應而導入聚合性基，使該聚合性基聚合。 A polymer having a repeating unit containing the above equations (6) to (9) can be synthesized by introducing a hydroxyl group into any of A or D of the structure of the formula (1) in advance as a linker. The following compound is reacted to introduce a polymerizable group, and the polymerizable group is polymerized.
分子內含有通式(1)所表示之結構之聚合物可為僅由具有通式(1)所表示之結構之重複單元所構成的聚合物，亦可為包含具有其以外之結構之重複單元的聚合物。又，聚合物中所含有之具有通式(1)所表示之結構之重複單元可為單獨一種，亦可為兩種以上。作為不具有通式(1)所表示之結構之重複單元，可列舉由通常之共聚所使用之單體衍生者。例如，可列舉由乙烯、苯乙烯等具有乙烯性不飽和鍵之單體衍生之重複單元。 The polymer having a structure represented by the formula (1) in the molecule may be a polymer composed only of a repeating unit having a structure represented by the formula (1), or may be a repeating unit having a structure other than the above. Polymer. Further, the repeating unit having the structure represented by the formula (1) contained in the polymer may be used alone or in combination of two or more. The repeating unit having no structure represented by the formula (1) includes a monomer derivative which is used in usual copolymerization. For example, a repeating unit derived from a monomer having an ethylenically unsaturated bond such as ethylene or styrene may be mentioned.
[通式(1)所表示之化合物之合成方法] [Synthesis method of compound represented by general formula (1)]
通式(1)所表示之化合物可藉由將已知之反應組合而合成。例如，可按照以下流程合成。 The compound represented by the formula (1) can be synthesized by combining known reactions. For example, it can be synthesized according to the following process.
[化30]H-D-H+X-A → A-D-A [化30]H-D-H+X-A → A-D-A
關於上式之D及A之說明，可參照通式(1)之對應記載。上式之X表示鹵素原子，可列舉氟原子、氯原子、溴原子、碘原子，較佳為氯原子、溴原子、碘原子。 For the description of D and A in the above formula, the corresponding description of the general formula (1) can be referred to. X in the above formula represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom, a bromine atom, and an iodine atom are preferred.
通式(1)所表示之化合物中，例如通式(3)所表示之化合物可藉由以下之流程合成。其中，以下記載之流程為表示R11與R16、R12與R17、R13與R18、R14與R19、R15與R20相同之情形之合成法者。 Among the compounds represented by the formula (1), for example, the compound represented by the formula (3) can be synthesized by the following scheme. Here, the scheme described below is a synthesis method in which R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 are the same.
關於上式之R1~R8及R11~R20之說明，可參照通式(3)之對應記載。上式之X表示鹵素原子。 For the description of R 1 to R 8 and R 11 to R 20 in the above formula, the corresponding description of the general formula (3) can be referred to. X of the above formula represents a halogen atom.
上述兩個流程之反應為應用公知之反應者，可適當選擇公知之 反應條件使用。關於上述反應之詳細情況，可將後述合成例作為參考。又，通式(1)所表示之化合物亦可藉由將其他公知之合成反應組合而合成。 The reaction of the above two processes is to apply a well-known reaction, and the known one can be appropriately selected. The reaction conditions are used. Regarding the details of the above reaction, a synthesis example described later can be referred to. Further, the compound represented by the formula (1) can also be synthesized by combining other known synthesis reactions.
[有機發光元件] [Organic light-emitting element]
本發明之通式(1)所表示之化合物可用作有機發光元件之發光材料。因此，本發明之通式(1)所表示之化合物可作為發光材料而有效地用於有機發光元件之發光層。於通式(1)所表示之化合物中，包括放射延遲螢光之延遲螢光材料(延遲螢光體)。即，本發明亦提供：具有通式(1)所表示之結構之延遲螢光體之發明，將通式(1)所表示之化合物用作延遲螢光體之發明，以及使用通式(1)所表示之化合物發出延遲螢光之方法之發明。將此種化合物用作發光材料之有機發光元件具有放射延遲螢光、且發光效率較高之特徵。若列舉有機電致發光元件為例來對其原理進行說明，則如下所述。 The compound represented by the formula (1) of the present invention can be used as a light-emitting material of an organic light-emitting element. Therefore, the compound represented by the formula (1) of the present invention can be effectively used as a light-emitting material for the light-emitting layer of the organic light-emitting element. Among the compounds represented by the formula (1), a delayed fluorescent material (delayed phosphor) which emits delayed fluorescence is included. That is, the present invention also provides the invention of a delayed phosphor having the structure represented by the general formula (1), the invention of the compound represented by the general formula (1) as a delayed phosphor, and the use of the general formula (1) The invention is a method in which the compound represented by the method emits delayed fluorescence. An organic light-emitting element using such a compound as a light-emitting material has a feature of emitting delayed fluorescence and having high luminous efficiency. The principle of the organic electroluminescent device will be described as an example, as follows.
有機電致發光元件中，自正負兩電極對發光材料注入載子，產生激發狀態之發光材料而進行發光。通常，於載子注入型之有機電致發光元件之情形時，所產生之激子中，被激發成激發單重態者為25%，其餘75%被激發成激發三重態。因此，利用作為來自激發三重態之發光的磷光者能量之利用效率較高。然而，多數情況下，由於激發三重態之壽命較長，故而產生因激發狀態之飽和或激發三重態之激子間之相互作用導致之能量之失活，通常，磷光之量子產率不高。另一方面，延遲螢光材料藉由系間跨越等而使能量向激發三重態遷移後，由於三重態-三重態湮滅或者熱能之吸收而逆系間跨越成激發單重態，放射螢光。有機電致發光元件中，認為其中藉由熱能之吸收之熱活化型延遲螢光材料尤其有用。於將延遲螢光材料用於有機電致發光元件之情形時，激發單重態之激子如通常般放射螢光。另一方面，激發三重態之激子吸收器件所發出之熱，向激發單重態進行系間跨 越，放射螢光。此時，由於為來自激發單重態之發光，故為波長與螢光相同之發光，並且藉由自激發三重態向激發單重態之逆系間跨越，所產生之光之壽命(發光壽命)較通常之螢光或磷光長，故而作為較該等延遲之螢光而被觀察到。可將其定義為延遲螢光。若使用此種熱活化型之激子移動機制，則藉由在載子注入後經由熱能之吸收，可將通常僅產生25%之激發單重態之化合物之比率提昇至25%以上。若使用即便於未達100℃之較低溫度下亦發出較強螢光及延遲螢光之化合物，則由於因器件之熱而充分地產生自激發三重態向激發單重態之系間跨越而放射延遲螢光，故可飛躍性地提高發光效率。 In the organic electroluminescence device, a carrier is injected into the luminescent material from the positive and negative electrodes, and a luminescent material in an excited state is generated to emit light. Generally, in the case of a carrier-injection type organic electroluminescent device, among the excitons generated, 25% are excited to excite the singlet state, and the remaining 75% are excited to the excited triplet state. Therefore, the utilization efficiency of the phosphorer energy as the light emission from the excited triplet state is high. However, in most cases, since the lifetime of the excited triplet state is long, the energy is deactivated due to the interaction between the excited state or the excited triplet excitons. Generally, the quantum yield of phosphorescence is not high. On the other hand, after the delayed fluorescent material migrates energy to the excited triplet state by inter-system crossing or the like, the triplet-triplet state quenching or the absorption of thermal energy crosses the intersystem to the excited singlet state, and emits fluorescence. Among the organic electroluminescent elements, heat-activated delayed fluorescent materials in which absorption by thermal energy is considered are particularly useful. In the case where a delayed fluorescent material is used for the organic electroluminescent element, the singlet excitons are excited to emit fluorescence as usual. On the other hand, the exciton that excites the triplet absorbs the heat emitted by the device, and the inter-system cross is excited to the excited singlet state. The more, the fluorescent light. At this time, since it is the luminescence from the excited singlet state, it is the same luminescence of the wavelength as the fluorescence, and the lifetime of the generated light (luminous lifetime) is compared by the inverse intersystem crossing of the self-excited triplet state to the excited singlet state. Usually, the fluorescence or phosphorescence is long, so it is observed as the fluorescence of the delay. It can be defined as delayed fluorescence. If such a heat-activated exciton shift mechanism is used, the ratio of the compound which normally produces only 25% of the excited singlet state can be increased to 25% or more by absorption of thermal energy after the carrier is injected. If a compound that emits strong fluorescence and delayed fluorescence even at a lower temperature of less than 100 ° C is used, it is sufficiently radiated due to the heat of the device to generate a self-excited triplet to the excited singlet. Delayed fluorescence, so it can dramatically improve luminous efficiency.
藉由將本發明之通式(1)所表示之化合物用作發光層之發光材料，可提供有機光致發光元件(有機PL(Photoluminescence，光致發光)元件)或有機電致發光元件(有機EL元件)等優異之有機發光元件。此時，本發明之通式(1)所表示之化合物亦可作為所謂輔助摻雜劑而具有輔助發光層所含有之其他發光材料之發光的功能。即，發光層所含有之本發明之通式(1)所表示之化合物亦可具有發光層所含有之主體材料之最低激發單重態能階與發光層所含有之其他發光材料之最低激發單重態能階之間的最低激發單重態能階。 By using the compound represented by the general formula (1) of the present invention as a light-emitting material of a light-emitting layer, an organic photoluminescence element (organic PL (photoluminescence) element) or an organic electroluminescence element (organic) can be provided. An excellent organic light-emitting element such as an EL element). In this case, the compound represented by the formula (1) of the present invention may also function as a so-called auxiliary dopant to have light emission of the other luminescent material contained in the auxiliary luminescent layer. That is, the compound represented by the formula (1) of the present invention contained in the light-emitting layer may have the lowest excited singlet energy level of the host material contained in the light-emitting layer and the lowest excited singlet state of the other light-emitting materials contained in the light-emitting layer. The lowest excited singlet energy level between energy levels.
有機光致發光元件具有於基板上至少形成發光層之結構。又，有機電致發光元件具有至少形成陽極、陰極及陽極與陰極之間的有機層之結構。有機層至少含有發光層，可僅由發光層所構成，亦可除了發光層以外具有1層以上之有機層。作為此種其他有機層，可列舉電洞傳輸層、電洞注入層、電子阻擋層、電洞阻擋層、電子注入層、電子傳輸層、激子阻擋層等。電洞傳輸層亦可為具有電洞注入功能之電洞注入傳輸層，電子傳輸層亦可為具有電子注入功能之電子注入傳輸層。將具體之有機電致發光元件之結構例示於圖1。圖1中，1表示基板，2表示陽極，3表示電洞注入層，4表示電洞傳輸層，5表示發光 層，6表示電子傳輸層，7表示陰極。 The organic photoluminescent element has a structure in which at least a light-emitting layer is formed on a substrate. Further, the organic electroluminescence device has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed. The organic layer contains at least a light-emitting layer, and may be composed only of the light-emitting layer, or may have one or more organic layers in addition to the light-emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may also be a hole injection transport layer having a hole injection function, and the electron transport layer may also be an electron injection transport layer having an electron injection function. A specific example of the structure of the organic electroluminescence device is shown in Fig. 1. In Fig. 1, 1 denotes a substrate, 2 denotes an anode, 3 denotes a hole injection layer, 4 denotes a hole transport layer, and 5 denotes a light. Layer, 6 represents the electron transport layer, and 7 represents the cathode.
以下，對有機電致發光元件之各構件及各層進行說明。再者，基板及發光層之說明亦適用於有機光致發光元件之基板及發光層。 Hereinafter, each member and each layer of the organic electroluminescence device will be described. Furthermore, the description of the substrate and the light-emitting layer is also applicable to the substrate and the light-emitting layer of the organic photoluminescent device.
(基板) (substrate)
本發明之有機電致發光元件較佳為由基板所支持。關於該基板，並無特別限制，只要為自先前以來有機電致發光元件所慣用者即可，例如可使用包含玻璃、透明塑膠、石英、矽等者。 The organic electroluminescent device of the present invention is preferably supported by a substrate. The substrate is not particularly limited as long as it is conventionally used for an organic electroluminescence device. For example, glass, transparent plastic, quartz, ruthenium or the like can be used.
(陽極) (anode)
作為有機電致發光元件之陽極，可較佳地使用將功函數較大(4eV以上)之金屬、合金、導電性化合物及該等之混合物作為電極材料者。作為此種電極材料之具體例，可列舉：Au等金屬、CuI、氧化銦錫(ITO，Indium Tin Oxide)、SnO2、ZnO等導電性透明材料。又，亦可使用IDIXO(In2O3-ZnO)等非晶質且可製作透明導電膜之材料。關於陽極，可藉由蒸鍍或濺鍍等方法使該等電極材料形成薄膜，利用光微影法形成所需之形狀之圖案，或者於不大需要圖案精度之情形時(100μm以上程度)，亦可於上述電極材料之蒸鍍或濺鍍時介隔所需形狀之遮罩而形成圖案。或者，於使用如有機導電性化合物般可塗佈之材料之情形時，亦可使用印刷方式、塗佈方式等濕式成膜法。於自該陽極提取發光之情形時，較理想為使透過率大於10%，又，陽極之薄片電阻較佳為數百Ω/□以下。進而，膜厚雖亦取決於材料，然通常係於10~1000nm、較佳為10~200nm之範圍內選擇。 As the anode of the organic electroluminescence device, a metal having a large work function (4 eV or more), an alloy, a conductive compound, and a mixture thereof can be preferably used as the electrode material. Specific examples of such an electrode material include a conductive transparent material such as a metal such as Au, CuI, indium tin oxide (ITO, Indium Tin Oxide), SnO 2 or ZnO. Further, a material which is amorphous and can be made into a transparent conductive film such as IDIXO (In 2 O 3 -ZnO) can also be used. Regarding the anode, the electrode materials can be formed into a thin film by vapor deposition or sputtering, and a pattern of a desired shape can be formed by photolithography, or when pattern precision is not required (100 μm or more). It is also possible to form a pattern by masking a desired shape during vapor deposition or sputtering of the above electrode material. Alternatively, in the case of using a material which can be applied as an organic conductive compound, a wet film formation method such as a printing method or a coating method can also be used. In the case where light is extracted from the anode, it is preferable that the transmittance is more than 10%, and the sheet resistance of the anode is preferably several hundred Ω/□ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
(陰極) (cathode)
另一方面，作為陰極，使用將功函數較小(4eV以下)之金屬(稱為電子注入性金屬)、合金、導電性化合物及該等之混合物作為電極材料者。作為此種電極材料之具體例，可列舉：鈉、鈉-鉀合金、鎂、鋰、鎂/銅混合物、鎂/銀混合物、鎂/鋁混合物、鎂/銦混合物、鋁/氧 化鋁(Al2O3)混合物、銦、鋰/鋁混合物、稀土類金屬等。該等之中，就電子注入性及對氧化等之耐久性之方面而言，較佳為電子注入性金屬與作為功函數之值大於其且穩定之金屬的第二金屬之混合物，例如，鎂/銀混合物、鎂/鋁混合物、鎂/銦混合物、鋁/氧化鋁(Al2O3)混合物、鋰/鋁混合物、鋁等。陰極可藉由利用蒸鍍或濺鍍等方法使該等電極材料形成薄膜而製作。又，陰極之薄片電阻較佳為數百Ω/□以下，膜厚係於通常10nm~5μm、較佳為50~200nm之範圍內選擇。再者，為了使發出之光透過，只要有機電致發光元件之陽極或陰極之任一者為透明或半透明，則發光亮度提高而良好。 On the other hand, as the cathode, a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an alloy, a conductive compound, and a mixture thereof are used as the electrode material. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium/copper mixture, magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, and aluminum/aluminum oxide (Al 2 ). O 3 ) a mixture, indium, a lithium/aluminum mixture, a rare earth metal, or the like. Among these, in terms of electron injectability and durability against oxidation or the like, a mixture of an electron injecting metal and a second metal having a work function value larger than the stable metal, for example, magnesium, is preferable. / Silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/alumina (Al 2 O 3 ) mixture, lithium/aluminum mixture, aluminum, and the like. The cathode can be produced by forming the electrode material into a thin film by a method such as vapor deposition or sputtering. Further, the sheet resistance of the cathode is preferably several hundred Ω/□ or less, and the film thickness is selected in the range of usually 10 nm to 5 μm, preferably 50 to 200 nm. Further, in order to transmit the emitted light, as long as either the anode or the cathode of the organic electroluminescent element is transparent or translucent, the luminance of the light is improved and is good.
又，藉由將陽極之說明中列舉之導電性透明材料用於陰極，可製作透明或半透明之陰極，藉由應用其，可製作陽極與陰極兩者具有透過性之元件。 Further, by using the conductive transparent material exemplified in the description of the anode for the cathode, a transparent or translucent cathode can be produced, and by applying it, an element having permeability of both the anode and the cathode can be produced.
(發光層) (lighting layer)
發光層係藉由自陽極及陰極分別注入之電洞及電子再結合而產生激子後發光之層，可將發光材料單獨用於發光層中，較佳為包含發光材料及主體材料。作為發光材料，可使用選自通式(1)所表示之本發明之化合物群中之1種或2種以上。為了使本發明之有機電致發光元件及有機光致發光元件表現出較高發光效率，重要的是將發光材料所產生之單重態激子及三重態激子封閉於發光材料中。因此，較佳為於發光層中除了發光材料以外，亦使用主體材料。作為主體材料，可使用激發單重態能量、激發三重態能量之至少任一者具有高於本發明之發光材料之值的有機化合物。其結果，可將本發明之發光材料所產生之單重態激子及三重態激子封閉於本發明之發光材料之分子中，可充分地發揮出其發光效率。然而，亦有即便無法充分地封閉單重態激子及三重態激子，亦可獲得較高發光效率之情形，故只要為可實現較高發光效率之主體材料，則可無特別限制地用於本發明中。於本發明之 有機發光元件或有機電致發光元件中，發光係由發光層所含有之本發明之發光材料所產生。該發光包含螢光發光及延遲螢光發光兩者。但發光之一部分亦可包含來自主體材料之發光。 The luminescent layer is formed by recombining holes and electrons injected from the anode and the cathode respectively to generate an exciton light-emitting layer. The luminescent material may be used alone in the luminescent layer, preferably comprising a luminescent material and a host material. As the luminescent material, one or two or more selected from the group of compounds of the present invention represented by the formula (1) can be used. In order for the organic electroluminescent device and the organic photoluminescent device of the present invention to exhibit high luminous efficiency, it is important to block the singlet excitons and triplet excitons generated by the luminescent material in the luminescent material. Therefore, it is preferred to use a host material in addition to the luminescent material in the luminescent layer. As the host material, at least either of the excited singlet energy and the excited triplet energy may be used as an organic compound having a value higher than that of the luminescent material of the present invention. As a result, the singlet excitons and triplet excitons generated by the luminescent material of the present invention can be enclosed in the molecules of the luminescent material of the present invention, and the luminous efficiency can be sufficiently exhibited. However, even if the singlet excitons and the triplet excitons are not sufficiently blocked, a higher luminous efficiency can be obtained, so that it is not particularly limited as long as it is a host material capable of achieving high luminous efficiency. In the present invention. In the invention In the organic light-emitting device or the organic electroluminescence device, the light-emitting device is produced by the light-emitting material of the present invention contained in the light-emitting layer. The luminescence includes both fluorescent luminescence and delayed luminescence. However, a portion of the illumination may also include illumination from the host material.
於使用主體材料之情形時，作為發光材料之本發明之化合物於發光層中所含之量較佳為0.1重量%以上，更佳為1重量%以上，又，較佳為50重量%以下，更佳為20重量%以下，進而較佳為10重量%以下。 In the case of using a host material, the amount of the compound of the present invention as a light-emitting material in the light-emitting layer is preferably 0.1% by weight or more, more preferably 1% by weight or more, and still more preferably 50% by weight or less. More preferably, it is 20 weight% or less, More preferably, it is 10 weight% or less.
作為發光層之主體材料，較佳為具有電洞傳輸能力、電子傳輸能力，且可防止發光之長波長化，進而具有較高之玻璃轉移溫度之有機化合物。 As the host material of the light-emitting layer, an organic compound having a hole transporting ability and an electron-transporting ability and having a long wavelength of light emission and having a high glass transition temperature is preferable.
(注入層) (injection layer)
所謂注入層，意指為了降低驅動電壓或提高發光亮度而設置於電極與有機層間之層，有電洞注入層及電子注入層，亦可存在於陽極與發光層或電洞傳輸層之間、及陰極與發光層或電子傳輸層之間。注入層可視需要設置。 The injection layer means a layer provided between the electrode and the organic layer in order to lower the driving voltage or increase the luminance of the light, and has a hole injection layer and an electron injection layer, and may exist between the anode and the light-emitting layer or the hole transport layer. And between the cathode and the light emitting layer or the electron transport layer. The injection layer can be set as needed.
(阻擋層) (barrier layer)
阻擋層係可阻擋存在於發光層中之電荷(電子或電洞)及/或激子向發光層外擴散之層。電子阻擋層可配置於發光層及電洞傳輸層之間，阻擋電子朝電洞傳輸層之方向通過發光層。同樣地，電洞阻擋層可配置於發光層及電子傳輸層之間，阻擋電洞朝電子傳輸層之方向通過發光層。阻擋層又可用於阻擋激子向發光層之外側擴散。即，電子阻擋層、電洞阻擋層亦可分別兼具作為激子阻擋層之功能。本說明書中所述之電子阻擋層或激子阻擋層係以包含以一層具有電子阻擋層及激子阻擋層之功能之層的含義使用。 The barrier layer blocks the charge (electrons or holes) present in the light-emitting layer and/or the layer of excitons that diffuse out of the light-emitting layer. The electron blocking layer may be disposed between the light emitting layer and the hole transport layer to block electrons from passing through the light emitting layer in the direction of the hole transport layer. Similarly, the hole blocking layer may be disposed between the light emitting layer and the electron transport layer, and the blocking hole passes through the light emitting layer toward the electron transport layer. The barrier layer can in turn be used to block the diffusion of excitons to the outside of the luminescent layer. That is, the electron blocking layer and the hole blocking layer may each function as an exciton blocking layer. The electron blocking layer or exciton blocking layer described in the present specification is used in the sense of including a layer having a function of an electron blocking layer and an exciton blocking layer.
(電洞阻擋層) (hole blocking layer)
所謂電洞阻擋層，廣義上具有電子傳輸層之功能。電洞阻擋層 有一面傳輸電子、一面阻擋電洞到達電子傳輸層之作用，藉此可提高發光層中之電子與電洞之再結合概率。作為電洞阻擋層之材料，可視需要使用下述電子傳輸層之材料。 The so-called hole blocking layer has a function of an electron transport layer in a broad sense. Hole barrier One side transmits electrons and blocks the holes from reaching the electron transport layer, thereby increasing the probability of recombination of electrons and holes in the light-emitting layer. As the material of the hole blocking layer, the material of the electron transport layer described below may be used as needed.
(電子阻擋層) (electronic barrier layer)
所謂電子阻擋層，廣義上具有傳輸電洞之功能。電子阻擋層有一面傳輸電洞、一面阻擋電子到達電洞傳輸層之作用，藉此可提高發光層中之電子與電洞再結合之概率。 The so-called electron blocking layer has a function of transmitting holes in a broad sense. The electron blocking layer has a function of transmitting a hole on one side and blocking electrons from reaching the hole transport layer, thereby increasing the probability of recombination of electrons and holes in the light-emitting layer.
(激子阻擋層) (exciton blocking layer)
所謂激子阻擋層，係指用以阻擋於發光層內因電洞與電子再結合而產生之激子擴散至電荷傳輸層之層，可藉由該層之***將激子有效率地封閉於發光層內，從而可提高元件之發光效率。激子阻擋層可鄰接於發光層而***至陽極側、陰極側之任一側，亦可同時***至兩側。即，於在陽極側具有激子阻擋層之情形時，可於電洞傳輸層與發光層之間，鄰接於發光層而***該層，於***至陰極側之情形時，可於發光層與陰極之間，鄰接於發光層而***該層。又，於陽極與鄰接於發光層之陽極側之激子阻擋層之間可具有電洞注入層或電子阻擋層等，於陰極與鄰接於發光層之陰極側之激子阻擋層之間可具有電子注入層、電子傳輸層、電洞阻擋層等。於配置阻擋層之情形時，較佳為用作阻擋層之材料之激發單重態能量及激發三重態能量之至少任一者高於發光材料之激發單重態能量及激發三重態能量。 The exciton blocking layer refers to a layer for blocking the diffusion of excitons generated by recombination of holes and electrons into the charge transport layer in the light-emitting layer, and the excitons can be efficiently enclosed by the insertion of the layer. Within the layer, the luminous efficiency of the component can be improved. The exciton blocking layer may be inserted adjacent to the light emitting layer to either the anode side or the cathode side, or may be simultaneously inserted to both sides. That is, in the case where the exciton blocking layer is provided on the anode side, the layer may be inserted between the hole transport layer and the light-emitting layer adjacent to the light-emitting layer, and when inserted into the cathode side, the light-emitting layer may be The layers are inserted between the cathodes adjacent to the light-emitting layer. Further, a hole injection layer or an electron blocking layer may be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer, and may have between the cathode and the exciton blocking layer adjacent to the cathode side of the light emitting layer. Electron injection layer, electron transport layer, hole blocking layer, and the like. In the case of arranging the barrier layer, it is preferred that at least one of the excited singlet energy and the excited triplet energy of the material used as the barrier layer is higher than the excited singlet energy and the excited triplet energy of the luminescent material.
(電洞傳輸層) (hole transport layer)
所謂電洞傳輸層，包含具有傳輸電洞之功能之電洞傳輸材料，電洞傳輸層可設置單層或複數層。 The hole transport layer includes a hole transport material having a function of transmitting a hole, and the hole transport layer may be provided with a single layer or a plurality of layers.
作為電洞傳輸材料，係具有電洞之注入或傳輸、電子之障壁性之任一種者，可為有機物、無機物之任一種。作為可使用之公知之電洞傳輸材料，例如可列舉：***衍生物、二唑衍生物、咪唑衍生 物、咔唑衍生物、吲哚咔唑衍生物、聚芳基烷烴衍生物、吡唑啉衍生物及吡唑啉酮衍生物、苯二胺衍生物、芳基胺衍生物、胺基取代查爾酮衍生物、唑衍生物、苯乙烯基蒽衍生物、茀酮衍生物、腙衍生物、茋衍生物、矽氮烷衍生物、苯胺系共聚物、或導電性高分子低聚物、尤其是噻吩低聚物等，較佳為使用卟啉化合物、芳香族三級胺化合物及苯乙烯基胺化合物，更佳為使用芳香族三級胺化合物。 The hole transporting material may be any one of an organic substance and an inorganic substance, and may be any one of an injection or a transmission of a hole and a barrier property of an electron. As a known hole transporting material which can be used, for example, a triazole derivative can be cited. Diazole derivatives, imidazole derivatives, carbazole derivatives, carbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamines Derivatives, amine-substituted chalcone derivatives, An azole derivative, a styryl hydrazine derivative, an anthrone derivative, an anthracene derivative, an anthracene derivative, a decazane derivative, an aniline copolymer, or a conductive polymer oligomer, especially a thiophene oligomer Preferably, a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound are used, and an aromatic tertiary amine compound is more preferably used.
(電子傳輸層) (electronic transport layer)
所謂電子傳輸層，包含具有傳輸電子之功能之材料，電子傳輸層可設置單層或複數層。 The electron transport layer includes a material having a function of transmitting electrons, and the electron transport layer may be provided with a single layer or a plurality of layers.
作為電子傳輸材料(亦有兼為電洞阻擋材料之情形)，只要具有將自陰極注入之電子傳遞至發光層之功能即可。作為可使用之電子傳輸層，例如可列舉：硝基取代茀衍生物、聯苯醌衍生物、二氧化噻喃衍生物、碳二醯亞胺、亞茀基甲烷衍生物、蒽醌二甲烷及蒽酮衍生物、二唑衍生物等。進而，上述二唑衍生物中，將二唑環之氧原子取代為硫原子而成之噻二唑衍生物、具有作為拉電子基而為人所知之喹啉環之喹啉衍生物亦可用作電子傳輸材料。進而，亦可使用將該等材料導入至高分子鏈中、或將該等材料設為高分子之主鏈之高分子材料。 As the electron transporting material (which is also a case of a hole blocking material), it is only required to have a function of transferring electrons injected from the cathode to the light emitting layer. Examples of the electron transporting layer which can be used include a nitro-substituted anthracene derivative, a biphenyl hydrazine derivative, a thiopyran derivative, a carbodiimide, a fluorenylene methane derivative, and quinodimethane. Anthrone derivative, Diazole derivatives and the like. Further, the above Among the oxadiazole derivatives, A thiadiazole derivative in which an oxygen atom of a oxazolyl ring is substituted with a sulfur atom, and a quinine which is known as a pull electron group Quinone ring The porphyrin derivative can also be used as an electron transporting material. Further, a polymer material in which the materials are introduced into the polymer chain or the materials are used as the main chain of the polymer may be used.
於製作有機電致發光元件之時，亦可將通式(1)所表示之化合物不僅用於發光層，而且亦用於發光層以外之層。此時，發光層所使用之通式(1)所表示之化合物與發光層以外之層所使用之通式(1)所表示之化合物可相同，亦可不同。例如，上述注入層、阻擋層、電洞阻擋層、電子阻擋層、激子阻擋層、電洞傳輸層、電子傳輸層等中亦可使用通式(1)所表示之化合物。該等層之製膜方法並無特別限定，可利用乾式製程、濕式製程之任一種製作。 When the organic electroluminescent device is produced, the compound represented by the formula (1) can be used not only for the light-emitting layer but also for the layer other than the light-emitting layer. In this case, the compound represented by the formula (1) used in the light-emitting layer may be the same as or different from the compound represented by the formula (1) used for the layer other than the light-emitting layer. For example, a compound represented by the formula (1) can also be used in the above injection layer, barrier layer, hole barrier layer, electron blocking layer, exciton blocking layer, hole transport layer, electron transport layer and the like. The film forming method of the layers is not particularly limited, and it can be produced by any of a dry process or a wet process.
以下，具體地例示可用於有機電致發光元件之較佳材料。但本 發明中可使用之材料並不受以下之例示化合物之限定性解釋。又，即便為作為具有特定功能之材料而例示之化合物，亦可轉用作具有其他功能之材料。再者，以下之例示化合物之結構式中之R、R2~R7分別獨立表示氫原子或取代基。n表示3~5之整數。 Hereinafter, preferred materials which can be used for the organic electroluminescent element are specifically exemplified. However, materials which can be used in the present invention are not limited by the following exemplified compounds. Further, even a compound exemplified as a material having a specific function can be used as a material having other functions. Further, in the structural formulae of the following exemplified compounds, R, R 2 to R 7 each independently represent a hydrogen atom or a substituent. n represents an integer from 3 to 5.
首先，列舉亦可用作發光層之主體材料之較佳化合物。 First, preferred compounds which can also be used as a host material for the light-emitting layer are listed.
其次，列舉可用作電洞注入材料之較佳化合物例。 Next, an example of a preferred compound which can be used as a hole injecting material is listed.
其次，列舉可用作電洞傳輸材料之較佳化合物例。 Next, examples of preferred compounds which can be used as a hole transporting material are listed.
其次，列舉可用作電子阻擋材料之較佳化合物例。 Next, examples of preferred compounds which can be used as electron blocking materials are listed.
其次，列舉可用作電洞阻擋材料之較佳化合物例。 Next, an example of a preferred compound which can be used as a barrier material for a hole is listed.
其次，列舉可用作電子傳輸材料之較佳化合物例。 Next, examples of preferred compounds which can be used as electron transport materials are listed.
其次，列舉可用作電子注入材料之較佳化合物例。 Next, examples of preferred compounds which can be used as electron injecting materials are listed.
列舉作為可進一步添加之材料之較佳化合物例。例如，可想到作為穩定材料而添加等。 Examples of preferred compounds are listed as further addable materials. For example, it is conceivable to add as a stabilizing material or the like.
藉由上述方法所製作之有機電致發光元件係藉由在所獲得之元件之陽極與陰極之間施加電場而發光。此時，若為藉由激發單重態能量所得之發光，則與其能階相對應之波長之光係作為螢光發光及延遲螢光發光而被確認到。又，若為藉由激發三重態能量所得之發光，則與其能階相對應之波長係作為磷光而被確認到。通常之螢光之螢光壽命比延遲螢光發光短，故而發光壽命可以螢光與延遲螢光加以區分。 The organic electroluminescent device produced by the above method emits light by applying an electric field between the anode and the cathode of the obtained device. At this time, if the luminescence obtained by exciting the singlet energy is used, the light of the wavelength corresponding to the energy level is confirmed as the luminescence and the delayed luminescence. Further, if the luminescence obtained by exciting the triplet energy is used, the wavelength corresponding to the energy level is confirmed as phosphorescence. Generally, the fluorescent lifetime of fluorescent light is shorter than that of delayed fluorescent light, so that the luminous lifetime can be distinguished by fluorescent and delayed fluorescent.
另一方面，關於磷光，如本發明之化合物般之通常之有機化合物之激發三重態能量不穩定而轉變為熱等，壽命較短而立刻失活，故而於室溫下幾乎無法觀察到。為了測定通常之有機化合物之激發三重態能量，可藉由觀測極低溫之條件下之發光而測定。 On the other hand, regarding phosphorescence, the excited triplet energy of a usual organic compound such as the compound of the present invention is unstable and converted into heat, etc., and the life is short and immediately deactivated, so that it is hardly observed at room temperature. In order to measure the excited triplet energy of a typical organic compound, it can be measured by observing the luminescence under extremely low temperature conditions.
本發明之有機電致發光元件可應用於單一元件、包含以陣列狀配置之結構之元件、將陽極及陰極以X-Y矩陣狀配置之結構之任一種。根據本發明，藉由使發光層中含有通式(1)所表示之化合物，可獲得發光效率較大改善之有機發光元件。本發明之有機電致發光元件 等有機發光元件可進而應用於各種用途中。例如，可使用本發明之有機電致發光元件來製造有機電致發光顯示裝置，關於詳細情況，可參照時任靜士、安達千波矢、村田英幸共著之「有機EL顯示器」(Ohm公司)。又，尤其是本發明之有機電致發光元件亦可應用於需求較大之有機電致發光照明或背光裝置。 The organic electroluminescence device of the present invention can be applied to any one of a single element, an element including a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an X-Y matrix. According to the invention, by including the compound represented by the formula (1) in the light-emitting layer, an organic light-emitting device having improved luminous efficiency can be obtained. Organic electroluminescent device of the invention The organic light-emitting element can be further applied to various uses. For example, an organic electroluminescence display device can be produced by using the organic electroluminescence device of the present invention. For details, refer to the "Organic EL Display" (Ohm Corporation) co-authored by Jing Shi, Anda Qianbo, and Murata Yoshiyuki. Further, in particular, the organic electroluminescence device of the present invention can also be applied to an organic electroluminescence illumination or a backlight device which is in great demand.
以下列舉合成例及實施例來進一步具體地說明本發明之特徵。以下所示之材料、處理內容、處理順序等只要不偏離本發明之主旨，則可適當變更。因此，本發明之範圍不應受以下所示之具體例之限定性解釋。 The features of the present invention will be further specifically described below by way of Synthesis Examples and Examples. The materials, processing contents, processing procedures, and the like shown below may be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the invention should not be construed as limited by the specific examples shown below.
再者，各材料之單重態能量(ES1)與三重態能量(ET1)之差(△EST)係利用以下之方法算出單重態能量(ES1)及三重態能量，並根據△EST=ES1-ET1求出者。 Furthermore, the difference between the singlet energy (E S1 ) and the triplet energy (E T1 ) of each material (ΔE ST ) is calculated by the following method to calculate singlet energy (E S1 ) and triplet energy, and according to ΔE ST = E S1 - E T1 is the winner.
(1)單重態能量ES1 (1) Singlet energy E S1
藉由將測定對象化合物與mCBP以測定對象化合物之濃度成為6重量%之方式進行共蒸鍍，而於Si基板上製作厚度100nm之試樣。於常溫(300 K)下測定該試樣之螢光光譜。藉由將激發光剛入射後至入射後100奈秒之發光進行加算，獲得將縱軸設為發光強度、將橫軸設為波長之螢光光譜。螢光光譜係將縱軸設為發光，將橫軸設為波長。相對於該發光光譜之短波側之上升畫切線，求出該切線與橫軸之交點之波長值λedge[nm]。將利用以下所示之換算式使該波長值換算為能量值而得之值設為ES1。 A sample having a thickness of 100 nm was formed on the Si substrate by co-evaporation so that the concentration of the measurement target compound and mCBP were 6% by weight. The fluorescence spectrum of the sample was measured at room temperature (300 K). The addition of the excitation light to the light emission of 100 nanoseconds after the incident is performed, and a fluorescence spectrum in which the vertical axis is the emission intensity and the horizontal axis is the wavelength is obtained. In the fluorescence spectrum, the vertical axis is set to emit light, and the horizontal axis is set to wavelength. The wavelength value λedge [nm] of the intersection of the tangent line and the horizontal axis is obtained by plotting the rising line on the short-wave side of the luminescence spectrum. The value obtained by converting the wavelength value into an energy value by the conversion formula shown below is set to E S1 .
換算式：ES1[eV]=1239.85/λedge Conversion formula: E S1 [eV]=1239.85/λedge
於發光光譜之測定中，使用氮雷射(Lasertechnik Berlin公司製造，MNL200)作為激發光源，使用超高速掃描照相機(Hamamatsu Photonics公司製造，C4334)作為檢測器。 In the measurement of the luminescence spectrum, a nitrogen laser (manufactured by Lasertechnik Berlin, MNL200) was used as an excitation light source, and an ultrahigh-speed scanning camera (manufactured by Hamamatsu Photonics Co., Ltd., C4334) was used as a detector.
(2)三重態能量ET1 (2) Triplet energy E T1
將與單重態能量ES1相同之試樣冷卻至5[K]，將激發光(337nm)照射於磷光測定用試樣，使用超高速掃描照相機，測定磷光強度。藉由將激發光入射後1毫秒至入射後10毫秒之發光進行加算，獲得將縱軸設為發光強度、將橫軸設為波長之磷光光譜。相對於該磷光光譜之短波長側之上升畫切線，求出該切線與橫軸之交點之波長值λedge[nm]。將利用以下所示之換算式使該波長值換算為能量值而得之值設為ET1． The sample having the same singlet energy E S1 was cooled to 5 [K], and the excitation light (337 nm) was irradiated to the sample for phosphorescence measurement, and the phosphorescence intensity was measured using an ultrahigh-speed scanning camera. By adding the light emission from 1 millisecond after the excitation light is incident to 10 milliseconds after the incident, a phosphorescence spectrum in which the vertical axis is the emission intensity and the horizontal axis is the wavelength is obtained. The wavelength value λedge [nm] of the intersection of the tangent line and the horizontal axis is obtained with respect to the rising tangent of the short-wavelength side of the phosphorescence spectrum. The value obtained by converting the wavelength value into an energy value by the conversion formula shown below is set to E T1 .
換算式：ET1[eV]=1239.85/λedge Conversion formula: E T1 [eV]=1239.85/λedge
相對於磷光光譜之短波長側之上升之切線係如下般畫出。於在光譜曲線上自磷光光譜之短波長側移動至光譜之極大值中最為短波長側之極大值時，朝長波長側考慮曲線上之各點之切線。該切線隨著曲線上升(即，隨著縱軸增大)，斜率增大。將於該斜率之值取得極大值之點畫出之切線設為相對於該磷光光譜之短波長側之上升之切線。 The tangent to the rise on the short wavelength side of the phosphorescence spectrum is as follows. When moving from the short-wavelength side of the phosphorescence spectrum to the maximum value of the shortest wavelength side of the maximum value of the spectrum on the spectral curve, the tangent of each point on the curve is considered toward the long wavelength side. The tangent increases as the curve rises (ie, as the vertical axis increases). The tangent drawn at the point where the value of the slope is maximized is set as the tangent to the rise on the short wavelength side of the phosphorescence spectrum.
再者，具有光譜之最大波峰強度之10%以下之波峰強度之極大點不包含於上述最為短波長側之極大值中，將於最接近最為短波長側之極大值且斜率之值取得極大值之點畫出之切線設為相對於該磷光光譜之短波長側之上升之切線。 Furthermore, the maximum point of the peak intensity having 10% or less of the maximum peak intensity of the spectrum is not included in the maximum value on the shortest wavelength side, and the maximum value closest to the shortest wavelength side and the value of the slope are maximized. The tangent drawn by the point is set as a tangent to the rise of the short wavelength side of the phosphorescence spectrum.
(合成例1)化合物1之合成 (Synthesis Example 1) Synthesis of Compound 1
於經氮氣置換之二口燒瓶添加5,10-二氫吩嗪(364mg，2.00mmol)、2-(4-溴苯基)-4,6-二苯基-1,3,5-三(1.71g，4.40mmol)、碳酸鉀(1.66g，12.0mmol)、甲苯20ml，於室溫下攪拌10分鐘。於其中添加乙酸鈀(II)(26.9mg，0.12mmol)、三-第三丁基膦(89.0mg，0.44mmol)、甲苯20ml之混合溶液，進行24小時加熱、回流。放置冷卻至室溫後，添加氯仿及鹽水，將有機層分液、萃取。添加無水硫酸鎂進行脫水，於減壓下將溶劑蒸餾去除，獲得紅色固體。利用己烷清洗固體，於減壓下進行乾燥，藉此獲得作為目標物之5,10-雙{4-(2,4-二苯基-1,3,5-三)-苯基}-吩嗪(產量：1.52g，產率：95.5%)。 Add 5,10-dihydrogen to a nitrogen-substituted two-necked flask Phenazine (364 mg, 2.00 mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-tri (1.71 g, 4.40 mmol), potassium carbonate (1.66 g, 12.0 mmol), 20 ml of toluene, and stirred at room temperature for 10 min. A mixed solution of palladium (II) acetate (26.9 mg, 0.12 mmol), tri-tert-butylphosphine (89.0 mg, 0.44 mmol), and toluene (20 ml) was added thereto, and the mixture was heated and refluxed for 24 hours. After standing to cool to room temperature, chloroform and brine were added, and the organic layer was separated and extracted. Anhydrous magnesium sulfate was added for dehydration, and the solvent was distilled off under reduced pressure to give a red solid. The solid was washed with hexane and dried under reduced pressure to obtain 5,10-bis{4-(2,4-diphenyl-1,3,5-tri) as a target. )-phenyl}- Phenazine (yield: 1.52 g, yield: 95.5%).
MALDI-MS(Matrix-Assisted Laser Desorption Ionization-Mass Spectrometry，基質輔助雷射脫附游離質譜)m/z計算值(C54H36N8)：797，實測值：797 MALDI-MS (Matrix-Assisted Laser Desorption Ionization-Mass Spectrometry) m/z calculated (C 54 H 36 N 8 ): 797, found: 797
元素分析：計算值(C54H36N8)：C為81.39，H為4.55，N為14.06，實測值：C為81.53，H為4.49，N為14.05。 Elemental analysis: Calculated value (C 54 H 36 N 8 ): C was 81.39, H was 4.55, N was 14.06, found: C was 81.53, H was 4.49, and N was 14.05.
(合成例2)化合物2之合成 (Synthesis Example 2) Synthesis of Compound 2
於經氮氣置換之二口燒瓶添加5,10-二氫吩嗪(364mg，2.00mmol)、4-溴苯甲腈(801mg，4.40mmol)、碳酸鉀(1.66g，12.0mmol)、甲苯20ml，於室溫下攪拌10分鐘。於其中添加乙酸鈀(II)(26.9mg，0.12mmol)、三-第三丁基膦(89.0mg，0.44mmol)、甲苯20ml之混合溶液，進行24小時加熱、回流。放置冷卻至室溫後，添加氯仿及鹽水，將有機層分液、萃取。若添加無水硫酸鎂進行脫水，於減壓下將溶劑蒸餾去除，則獲得橙色固體。利用己烷清洗固體，於減壓下進行乾燥，藉此獲得作為目標物之5,10-雙(4-氰基苯基)-吩嗪(產量：720mg，產率：93.6%)。 Add 5,10-dihydrogen to a nitrogen-substituted two-necked flask Phenazine (364 mg, 2.00 mmol), 4-bromobenzonitrile (801 mg, 4.40 mmol), potassium carbonate (1.66 g, 12.0 mmol), and 20 ml of toluene were stirred at room temperature for 10 min. A mixed solution of palladium (II) acetate (26.9 mg, 0.12 mmol), tri-tert-butylphosphine (89.0 mg, 0.44 mmol), and toluene (20 ml) was added thereto, and the mixture was heated and refluxed for 24 hours. After standing to cool to room temperature, chloroform and brine were added, and the organic layer was separated and extracted. When anhydrous magnesium sulfate was added for dehydration, the solvent was distilled off under reduced pressure to obtain an orange solid. The solid was washed with hexane and dried under reduced pressure to obtain 5,10-bis(4-cyanophenyl)- as a target. Phenazine (yield: 720 mg, yield: 93.6%).
MALDI-MS m/z計算值(C26H16N4)：384，實測值：384。 MALDI-MS m / z calcd for (C 26 H 16 N 4) : 384, Found: 384.
元素分析：計算值(C26H16N4)：C為81.23，H為4.20，N為14.57，實測值：C為81.27，H為4.11，N為14.49。 Elemental analysis: Calculated value (C 26 H 16 N 4 ): C was 81.23, H was 4.20, N was 14.57, found: C was 81.27, H was 4.11, and N was 14.49.
(合成例3)化合物3之合成 (Synthesis Example 3) Synthesis of Compound 3
於經氮氣置換之二口燒瓶添加5,10-二氫吩嗪(364mg，2.00mmol)、3-溴苯甲腈(801mg，4.40mmol)、碳酸鉀(1.66g，12.0mmol)、甲苯20ml，於室溫下攪拌10分鐘。於其中添加乙酸鈀(II)(26.9mg，0.12mmol)、三-第三丁基膦(89.0mg，0.44mmol)、甲苯20ml之混合溶液，進行24小時加熱、回流。放置冷卻至室溫後，添加氯仿及鹽水，將有機層分液、萃取。添加無水硫酸鎂進行脫水，於減壓下將溶劑蒸餾去除。藉由使用氯仿之矽膠管柱層析法將作為目標物之5,10-雙(3-氰基苯基)-吩嗪單離、純化(產量：704mg，產率：91.5%)。 Add 5,10-dihydrogen to a nitrogen-substituted two-necked flask Phenazine (364 mg, 2.00 mmol), 3-bromobenzonitrile (801 mg, 4.40 mmol), potassium carbonate (1.66 g, 12.0 mmol), and 20 ml of toluene were stirred at room temperature for 10 min. A mixed solution of palladium (II) acetate (26.9 mg, 0.12 mmol), tri-tert-butylphosphine (89.0 mg, 0.44 mmol), and toluene (20 ml) was added thereto, and the mixture was heated and refluxed for 24 hours. After standing to cool to room temperature, chloroform and brine were added, and the organic layer was separated and extracted. Anhydrous magnesium sulfate was added for dehydration, and the solvent was distilled off under reduced pressure. 5,10-bis(3-cyanophenyl)- as a target by using chloroform-tane column chromatography The phenazine was isolated and purified (yield: 704 mg, yield: 91.5%).
(合成例4)化合物5之合成 (Synthesis Example 4) Synthesis of Compound 5
於經氮氣置換之二口燒瓶添加5,10-二氫吩嗪(364mg，2.00mmol)、2-(4-溴苯基)-苯并噻唑(1.28g，4.40mmol)、碳酸鉀(1.66g，12.0mmol)、甲苯20ml，於室溫下攪拌10分鐘。於其中添加乙酸鈀(II)(26.9mg，0.12mmol)、三-第三丁基膦(89.0mg，0.44mmol)、甲苯20ml之混合溶液，進行24小時加熱、回流。放置冷卻至室溫後，添加氯仿及鹽水，將有機層分液、萃取。若添加無水硫酸鎂進行脫水，於減壓下將溶劑蒸餾去除，則獲得紅色固體。利用己烷清洗固體，於減壓下進行乾燥，藉此獲得作為目標物之5,10-雙{4-(2-苯并噻唑基)-苯基}-吩嗪(產量：1.01g，產率：84.0%)。 Add 5,10-dihydrogen to a nitrogen-substituted two-necked flask Phenazine (364 mg, 2.00 mmol), 2-(4-bromophenyl)-benzothiazole (1.28 g, 4.40 mmol), potassium carbonate (1.66 g, 12.0 mmol), 20 ml of toluene, stirred at room temperature for 10 min. . A mixed solution of palladium (II) acetate (26.9 mg, 0.12 mmol), tri-tert-butylphosphine (89.0 mg, 0.44 mmol), and toluene (20 ml) was added thereto, and the mixture was heated and refluxed for 24 hours. After standing to cool to room temperature, chloroform and brine were added, and the organic layer was separated and extracted. When anhydrous magnesium sulfate was added for dehydration, the solvent was distilled off under reduced pressure to obtain a red solid. The solid was washed with hexane and dried under reduced pressure to obtain 5,10-bis{4-(2-benzothiazolyl)-phenyl}- as a target. Phenazine (yield: 1.01 g, yield: 84.0%).
1H NMR(CDCl3,400MHz)δ：5.78(m,4H),6.34(m,4H),7.44(t,2H),7.54(t,2H),7.55(d,4H)7.95(d,2H),8.11(d,2H),8.35(d,4H) 1 H NMR (CDCl 3, 400MHz ) δ: 5.78 (m, 4H), 6.34 (m, 4H), 7.44 (t, 2H), 7.54 (t, 2H), 7.55 (d, 4H) 7.95 (d, 2H ), 8.11 (d, 2H), 8.35 (d, 4H)
MALDI-MS m/z計算值(C38H24N4S2)：601，實測值：600。 MALDI-MS m / z calcd for (C 38 H 24 N 4 S 2): 601, Found: 600.
元素分析：計算值(C38H24N4S2)：C為75.97，H為4.03，N為9.33，實測值：C為75.91，H為4.10，N為9.28。 Elemental analysis: Calculated (C 38 H 24 N 4 S 2 ): C was 75.97, H was 4.03, N was 9.33, found: C was 75.91, H was 4.10, and N was 9.28.
(合成例5)化合物6之合成 (Synthesis Example 5) Synthesis of Compound 6
於經氮氣置換之二口燒瓶添加5,10-二氫吩嗪(364mg，2.00mmol)、2-(4-溴苯基)-1-苯基-苯并咪唑(1.54g，4.40mmol)、碳酸鉀(1.66g，12.0mmol)、甲苯20ml，於室溫下攪拌10分鐘。於其中添加乙酸鈀(II)(26.9mg，0.12mmol)、三-第三丁基膦(89.0mg，0.44mmol)、甲苯20ml之混合溶液，進行24小時加熱、回流。放置冷卻至室溫後，添加氯仿及鹽水，將有機層分液、萃取。若添加無水硫酸鎂進行脫水，於減壓下將溶劑蒸餾去除，則獲得紅色固體。利用己烷清洗固體，於減壓下進行乾燥，藉此獲得作為目標物之5,10-雙[4-{2-(1-苯基)-苯并咪唑基}-苯基]-吩嗪(產量：1.40g，產率：97.3%)。 Add 5,10-dihydrogen to a nitrogen-substituted two-necked flask Phenazine (364 mg, 2.00 mmol), 2-(4-bromophenyl)-1-phenyl-benzimidazole (1.54 g, 4.40 mmol), potassium carbonate (1.66 g, 12.0 mmol), toluene 20 ml, Stir for 10 minutes at warm. A mixed solution of palladium (II) acetate (26.9 mg, 0.12 mmol), tri-tert-butylphosphine (89.0 mg, 0.44 mmol), and toluene (20 ml) was added thereto, and the mixture was heated and refluxed for 24 hours. After standing to cool to room temperature, chloroform and brine were added, and the organic layer was separated and extracted. When anhydrous magnesium sulfate was added for dehydration, the solvent was distilled off under reduced pressure to obtain a red solid. The solid was washed with hexane, and dried under reduced pressure, whereby 5,10-bis[4-{2-(1-phenyl)-benzimidazolyl}-phenyl]- as a target was obtained. Phenazine (yield: 1.40 g, yield: 97.3%).
1H NMR(CDCl3,400MHz)δ：7.28(d,8H),7.36(m,10H)7.39(d,4H),7.52(m,8H),7.89(d,4H) 1 H NMR (CDCl 3, 400MHz ) δ: 7.28 (d, 8H), 7.36 (m, 10H) 7.39 (d, 4H), 7.52 (m, 8H), 7.89 (d, 4H)
MALDI-MS m/z計算值(C50H34N6)：719，實測值：719。 MALDI-MS m / z calcd for (C 50 H 34 N 6) : 719, Found: 719.
元素分析：計算值(C50H34N6)：C為83.54，H為4.77，N為11.69，實測值：C為83.62，H為4.72，N為11.68。 Elemental analysis: Calculated value (C 50 H 34 N 6 ): C: 83.54, H: 4.77, N: 11.69, found: C: 83.62, H: 4.72, N: 11.68.
(實施例1)有機光致發光元件之製作及評價(溶液) (Example 1) Production and evaluation of an organic photoluminescent device (solution)
製備合成例1中所合成之化合物1之甲苯溶液(濃度10-5mol/L)，一面通入氮氣一面以300 K照射紫外光，結果觀測到586nm之螢光。又，於通入氮氣前後，藉由絕對PL量子產率測定裝置(Hamamatsu Photonics股份有限公司製造之Quantaurus-QY)以300 K測定甲苯溶液中之光致發光量子效率，結果通入氮氣前為3.4%，通入氮氣後為5.5%。 A toluene solution (concentration: 10 -5 mol/L) of the compound 1 synthesized in Synthesis Example 1 was prepared, and ultraviolet light was irradiated at 300 K while introducing nitrogen gas, and fluorescence of 586 nm was observed. Further, the photoluminescence quantum efficiency in the toluene solution was measured at 300 K by an absolute PL quantum yield measuring device (Quantaurus-QY manufactured by Hamamatsu Photonics Co., Ltd.) before and after the introduction of nitrogen gas, and the result was 3.4 before the introduction of nitrogen gas. %, 5.5% after passing nitrogen.
製備合成例2中所合成之化合物2之甲苯溶液(濃度10-5mol/L)代替化合物1，一面通入氮氣一面以300 K照射紫外光，結果觀測到545nm之螢光(通常螢光τp=6.28 ns、延遲螢光τd=1.88μs)。又，關於光致發光量子效率，通入氮氣前為3.3%，通入氮氣後為8.4%。 A toluene solution (concentration: 10 -5 mol/L) of the compound 2 synthesized in Synthesis Example 2 was prepared in place of the compound 1, and ultraviolet light was irradiated at 300 K while passing nitrogen gas, and fluorescence of 545 nm was observed (normally, fluorescence τ p = 6.28 ns, delayed fluorescence τ d = 1.88 μs). Further, the photoluminescence quantum efficiency was 3.3% before the introduction of nitrogen gas and 8.4% after the introduction of nitrogen gas.
製備合成例3中所合成之化合物3之甲苯溶液(濃度10-5mol/L)，一面通入氮氣一面以300 K照射紫外光，結果觀測到555nm之螢光。又，關於光致發光量子效率，通入氮氣前為1.9%，通入氮氣後為2.3%。 A toluene solution (concentration: 10 -5 mol/L) of the compound 3 synthesized in Synthesis Example 3 was prepared, and ultraviolet light was irradiated at 300 K while introducing nitrogen gas, and fluorescence of 555 nm was observed. Further, the photoluminescence quantum efficiency was 1.9% before the introduction of nitrogen gas and 2.3% after the introduction of nitrogen gas.
製備合成例5中所合成之化合物5之甲苯溶液(濃度10-5mol/L)，一面通入氮氣一面以300 K照射紫外光，結果觀測到605nm之螢光(τp=6.85 ns、τd=0.24μs)。又，關於光致發光量子效率，通入氮氣前為4.7%，通入氮氣後為9.7%。 A toluene solution (concentration: 10 -5 mol/L) of the compound 5 synthesized in Synthesis Example 5 was prepared, and ultraviolet light was irradiated at 300 K while passing nitrogen gas, and 605 nm fluorescence was observed (τ p = 6.85 ns, τ d =0.24 μs). Further, the photoluminescence quantum efficiency was 4.7% before the introduction of nitrogen gas and 9.7% after the introduction of nitrogen gas.
製備合成例6中所合成之化合物6之甲苯溶液(濃度10-5mol/L)，一面通入氮氣一面以300 K照射紫外光，結果觀測到554nm之螢光(τp=6.75 ns、τd=5.71μs)。又，關於光致發光量子效率，通入氮氣前為7.3%，通入氮氣後為31.4%。 A toluene solution (concentration: 10 -5 mol/L) of the compound 6 synthesized in Synthesis Example 6 was prepared, and ultraviolet light was irradiated at 300 K while passing nitrogen gas, and 554 nm fluorescence was observed (τ p = 6.75 ns, τ d = 5.71 μs). Further, the photoluminescence quantum efficiency was 7.3% before the introduction of nitrogen gas and 31.4% after the introduction of nitrogen gas.
(實施例2)有機光致發光元件之製作及評價(薄膜) (Example 2) Production and evaluation of organic photoluminescent device (film)
於矽基板上利用真空蒸鍍法，於真空度5.0×10-4Pa之條件下自不同之蒸鍍源蒸鍍化合物1及mCBP，以0.3nm/秒、100nm之厚度形成化合物1之濃度為6.0重量%之薄膜，製成有機光致發光元件。將50 K、100 K、150 K、200 K、250 K、300 K之各溫度下之暫態衰減曲線示於圖2。確認化合物1為熱活性型延遲螢光材料。300 K下之τp為6.24 ns，τd為0.14μs。 On the substrate, the compound 1 and mCBP were vapor-deposited from different vapor deposition sources under vacuum conditions of 5.0×10 −4 Pa on a substrate, and the concentration of the compound 1 was formed at a thickness of 0.3 nm/sec and 100 nm. 6.0% by weight of the film was made into an organic photoluminescent element. The transient attenuation curves at 50 K, 100 K, 150 K, 200 K, 250 K, and 300 K are shown in Fig. 2. Compound 1 was confirmed to be a thermally active delayed fluorescent material. The τ p at 300 K is 6.24 ns and the τ d is 0.14 μs.
使用化合物2代替化合物1，製作有機光致發光元件，同樣地進行測定。將50 K、100 K、150 K、200 K、250 K、300 K之各溫度下之暫態衰減曲線示於圖3。確認化合物2為熱活性型延遲螢光材料。300 K下之τp為6.83 ns，τd為6.69μs。又，使用與實施例1相同之測定裝置獲得之光致發光量子效率於300 K下為35.2%(通常螢光16.8%、延遲螢光18.4%)。△EST為0.10eV。 An organic photoluminescent device was produced by using Compound 2 instead of Compound 1, and the measurement was carried out in the same manner. The transient attenuation curves at 50 K, 100 K, 150 K, 200 K, 250 K, and 300 K are shown in Fig. 3. Compound 2 was confirmed to be a thermally active delayed fluorescent material. The τ p at 300 K is 6.83 ns and the τ d is 6.69 μs. Further, the photoluminescence quantum efficiency obtained by using the same measuring apparatus as in Example 1 was 35.2% at 300 K (normally 16.8% for fluorescence and 18.4% for delayed fluorescence). ΔE ST is 0.10 eV.
使用化合物5代替化合物1，製作有機光致發光元件，同樣地進行測定。將50 K、100 K、150 K、200 K、250 K、300 K之各溫度下之暫態衰減曲線示於圖4。確認化合物5為熱活性型延遲螢光材料。300 K下之τp為12.18 ns，τd為1.10μs。又，使用與實施例1相同之測定裝置獲得之光致發光量子效率於300 K下為33.0%(通常螢光20.6%、延遲螢光12.4%)。△EST為0.03eV。 An organic photoluminescent device was produced by using Compound 5 instead of Compound 1, and the measurement was carried out in the same manner. The transient attenuation curves at 50 K, 100 K, 150 K, 200 K, 250 K, and 300 K are shown in Fig. 4. Compound 5 was confirmed to be a thermally active delayed fluorescent material. The τ p at 300 K is 12.18 ns and the τ d is 1.10 μs. Further, the photoluminescence quantum efficiency obtained by using the same measuring apparatus as in Example 1 was 33.0% at 300 K (normally 20.6% for fluorescence and 12.4% for delayed fluorescence). ΔE ST is 0.03 eV.
使用化合物6代替化合物1，製作有機光致發光元件，同樣地進行測定。將50 K、100 K、150 K、200 K、250 K、300 K之各溫度下之暫態衰減曲線示於圖5。確認化合物6為熱活性型延遲螢光材料。300 K下之τp為4.12 ns，τd為53.00μs。又，使用與實施例1相同之測定裝置獲得之光致發光量子效率於300 K下為67.6%(通常螢光34.0%、延遲螢光33.6%)。△EST為0.19eV。 An organic photoluminescent device was produced by using Compound 6 instead of Compound 1, and the measurement was carried out in the same manner. The transient attenuation curves at 50 K, 100 K, 150 K, 200 K, 250 K, and 300 K are shown in Fig. 5. Compound 6 was confirmed to be a thermally active delayed fluorescent material. The τ p at 300 K is 4.12 ns and the τ d is 53.00 μs. Further, the photoluminescence quantum efficiency obtained by using the same measuring apparatus as in Example 1 was 67.6% at 300 K (normally 34.0% of fluorescence and 33.6% of delayed fluorescence). ΔE ST is 0.19 eV.
(實施例3)有機電致發光元件之製作及評價 (Example 3) Production and evaluation of organic electroluminescence device
於形成有膜厚100nm之包含銦錫氧化物(ITO)之陽極之玻璃基板上，利用真空蒸鍍法以真空度5.0×10-4Pa積層各薄膜。首先，於ITO上形成35nm之厚度之α-NPD。其次，自不同蒸鍍源共蒸鍍化合物1及CBP，形成15nm之厚度之層，製成發光層。此時，化合物1之濃度係設為2.0重量%。其次，形成65nm之厚度之TPBi，進而真空蒸鍍0.5nm之氟化鋰(LiF)，繼而，藉由以100nm之厚度蒸鍍鋁(Al)而形成陰極，製成有機電致發光元件。 On each of the glass substrates on which an anode containing indium tin oxide (ITO) having a film thickness of 100 nm was formed, each film was laminated by a vacuum deposition method at a degree of vacuum of 5.0 × 10 -4 Pa. First, α-NPD having a thickness of 35 nm was formed on ITO. Next, Compound 1 and CBP were co-evaporated from different vapor deposition sources to form a layer having a thickness of 15 nm to prepare a light-emitting layer. At this time, the concentration of the compound 1 was 2.0% by weight. Next, TPBi having a thickness of 65 nm was formed, and lithium fluoride (LiF) of 0.5 nm was vacuum-deposited, and then aluminum (Al) was vapor-deposited to a thickness of 100 nm to form a cathode, thereby preparing an organic electroluminescence device.
使用半導體參數分析儀(安捷倫科技公司製造，E5273A)、光功率計測定裝置(Newport公司製造，1930C)、及光學分光器(Ocean Optics公司製造，USB2000)測定所製造之有機電致發光元件，結果如圖6所示，確認到600nm之發光。將電流密度-電壓特性示於圖7。 The manufactured organic electroluminescence device was measured using a semiconductor parameter analyzer (manufactured by Agilent Technologies, Inc., E5273A), an optical power meter measuring device (manufactured by Newport Corporation, 1930C), and an optical spectroscope (manufactured by Ocean Optics, Inc., USB2000). As shown in Fig. 6, light emission of 600 nm was confirmed. The current density-voltage characteristics are shown in Fig. 7.
使用化合物2代替化合物1，製作發光層之化合物2之濃度為2.0重量%之有機電致發光元件、及發光層之化合物2之濃度為6.0重量%之有機電致發光元件。將發光光譜示於圖8，將電流密度-電壓特性示於圖9，將亮度-外部量子效率特性示於圖10，將電流密度-外部量子效率特性示於圖11。將化合物2用作發光材料之有機電致發光元件達成8.8%之較高外部量子效率。 Using the compound 2 instead of the compound 1, an organic electroluminescence device having a concentration of the compound 2 of the light-emitting layer of 2.0% by weight and an organic electroluminescence device having a concentration of the compound 2 of the light-emitting layer of 6.0% by weight were prepared. The luminescence spectrum is shown in Fig. 8, the current density-voltage characteristics are shown in Fig. 9, the luminance-external quantum efficiency characteristics are shown in Fig. 10, and the current density-external quantum efficiency characteristics are shown in Fig. 11. The organic electroluminescent element using Compound 2 as a light-emitting material achieved a high external quantum efficiency of 8.8%.
使用化合物6代替化合物1，製作發光層之化合物6之濃度為2.0重量%之有機電致發光元件。將發光光譜示於圖13，將電流密度-電壓特性示於圖14，將電流密度-外部量子效率特性示於圖15。將化合物6用作發光材料之有機電致發光元件達成11.3%之較高外部量子效率。又，將製作發光層之化合物6之濃度為6.0重量%之有機電致發光元件時之電流密度-外部量子效率特性示於圖12。該有機電致發光元件達成12.1%之較高外部量子效率。 Using Compound 6 instead of Compound 1, an organic electroluminescence device having a concentration of Compound 6 of the light-emitting layer of 2.0% by weight was prepared. The luminescence spectrum is shown in Fig. 13, the current density-voltage characteristics are shown in Fig. 14, and the current density-external quantum efficiency characteristics are shown in Fig. 15. The organic electroluminescent element using Compound 6 as a luminescent material achieved a higher external quantum efficiency of 11.3%. Further, the current density-external quantum efficiency characteristics of the organic electroluminescence device having a concentration of the compound 6 of the light-emitting layer of 6.0% by weight are shown in Fig. 12. The organic electroluminescent device achieved a high external quantum efficiency of 12.1%.
(比較例1)有機電致發光元件之製作及評價 (Comparative Example 1) Production and evaluation of organic electroluminescent elements
使用具有下述結構之比較化合物代替實施例3之化合物1，製作 有機電致發光元件。該有機電致發光元件完全不發光。 A compound having the following structure was used instead of the compound 1 of Example 3, and was produced. Organic electroluminescent element. The organic electroluminescent element does not emit light at all.
本發明之化合物可用作發光材料。因此，本發明之化合物可有效地用作有機電致發光元件等有機發光元件用之發光材料。於本發明之化合物之中，亦包括放射延遲螢光者，故而亦可提供發光效率較高之有機發光元件。因此，本發明之產業上之可利用性較高。 The compounds of the invention are useful as luminescent materials. Therefore, the compound of the present invention can be effectively used as a light-emitting material for an organic light-emitting element such as an organic electroluminescence device. Among the compounds of the present invention, radiation-delayed fluorescent light is also included, so that an organic light-emitting element having high luminous efficiency can be provided. Therefore, the industrial availability of the present invention is high.
1‧‧‧基板 1‧‧‧Substrate
2‧‧‧陽極 2‧‧‧Anode
3‧‧‧電洞注入層 3‧‧‧ hole injection layer
4‧‧‧電洞傳輸層 4‧‧‧ hole transport layer
5‧‧‧發光層 5‧‧‧Lighting layer
6‧‧‧電子傳輸層 6‧‧‧Electronic transport layer
7‧‧‧陰極 7‧‧‧ cathode
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| WO2020258651A1 (en) * | 2019-06-24 | 2020-12-30 | 武汉华星光电半导体显示技术有限公司 | Hole transport material, preparation method, and electroluminescent device |
| US11355713B2 (en) | 2019-06-24 | 2022-06-07 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Hole transport material, manufacturing method thereof, and electroluminescent device thereof |
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| WO2016111196A1 (en) * | 2015-01-08 | 2016-07-14 | 国立大学法人九州大学 | Compound, mixture, light-emitting layer, organic light-emitting element, and assist dopant |
| JP6769712B2 (en) | 2015-07-01 | 2020-10-14 | 国立大学法人九州大学 | Organic electroluminescence device |
| CN109196954B (en) | 2016-09-06 | 2021-01-05 | 九州有机光材股份有限公司 | Organic light emitting element |
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| KR20190070586A (en) | 2017-12-13 | 2019-06-21 | 엘지디스플레이 주식회사 | Compound for electron transporting material and organic light emitting diode including the same |
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| US20210305517A1 (en) | 2018-10-09 | 2021-09-30 | Kyulux, Inc. | Composition of matter for use in organic light-emitting diodes |
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| WO2021235549A1 (en) | 2020-05-22 | 2021-11-25 | 株式会社Kyulux | Compound, light-emitting material, and light-emitting element |
| WO2022025248A1 (en) | 2020-07-31 | 2022-02-03 | 株式会社Kyulux | Compound, light-emitting material, and light-emitting element |
| KR20230142466A (en) | 2021-02-04 | 2023-10-11 | 가부시키가이샤 큐럭스 | Compounds, light-emitting materials, and organic light-emitting devices |
| JP2022178366A (en) | 2021-05-20 | 2022-12-02 | 株式会社Kyulux | Organic light-emitting element |
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| WO2023282224A1 (en) | 2021-07-06 | 2023-01-12 | 株式会社Kyulux | Organic light-emitting element and design method therefor |
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| US11355713B2 (en) | 2019-06-24 | 2022-06-07 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Hole transport material, manufacturing method thereof, and electroluminescent device thereof |
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