TWI519534B - Thiocyanato or isothiocyanato substituted naphthalene diimide compounds and their use as n-type semiconductors - Google Patents

Description

經氰硫基或異氰硫基取代之萘二醯亞胺化合物及其作為n-型半導體之用途 Naphthalene diimide compound substituted with thiocyano or isocyanato group and use thereof as n-type semiconductor

有機發光二極體(OLED)、光伏打(OPV)及場效應電晶體(OFET)之最近發展為有機電子學領域開闢了許多機會。此領域之一個挑戰係研發具有環境上穩定的高遷移率電子傳輸(n-型)有機半導體之薄膜裝置。有機n-型材料之性能及穩定性顯著落後於其p-型對應物。發展有機n-型材料技術之一些挑戰包括其對環境條件(例如，空氣)之脆弱性及溶液可處理性。舉例而言，期望此等材料在常見溶劑中可溶以便於其能夠調配成用於便宜印刷製程之墨水。Recent developments in organic light-emitting diodes (OLEDs), photovoltaics (OPVs), and field effect transistors (OFETs) have opened up many opportunities for the field of organic electronics. One challenge in this area is the development of thin film devices with environmentally stable high mobility electron transport (n-type) organic semiconductors. The performance and stability of organic n-type materials lags significantly behind their p-type counterparts. Some of the challenges in developing organic n-type material technologies include their vulnerability to environmental conditions (eg, air) and solution handleability. For example, it is desirable that such materials be soluble in common solvents so that they can be formulated into inks for use in inexpensive printing processes.

最常見空氣穩定的n-型有機半導體包括全氟化銅酞菁(CuF₁₆Pc)、氟醯基寡聚噻吩(例如，DFCO-4TCO)、經N,N'-氟碳取代之萘二醯亞胺(例如，NDI-F、NDI-XF)、經氰基取代之苝二醯亞胺(例如，PDI-FCN₂)及經氰基取代之萘二醯亞胺(例如，NDI-8CN₂)。參見，例如，Bao等人(1998),J. Am. Chem. Soc,120: 207-208；de Oteyza等人(2005),Appl. Phys. Lett.,87: 183504；Schon等人(2000),Adv Mater. 12: 1539-1542；Ye等人(2005),Appl. Phys. Lett.,86: 253505；Yoon等人(2006),J. Am. Chem. Soc,128: 12851-12869；Tong等人(2006),J. Phys. Chem. B.,110: 17406-17413；Yuan等人(2004),Thin Solid Films,450: 316-319；Yoon等人(2005),J. Am. Chem. Soc,127: 1348-1349；Katz等人(2000),J. Am. Chem. Soc,122: 7787-7792；Katz等人(2000),Nature(London),404: 478-481；Katz等人(2001),Chem. Phys. Chem.,3: 167-172；Jung等人(2006),Appl. Phys. Lett.,88: 183102；Yoo等人(2006),IEEE Electron Device Lett.,27: 737-739；Jones等人(2004),Angew. Chem.,Int. Ed. Engl.,43: 6363-6366；及Jones等人(2007),J. Am. Chem. Soc,129: 15259-15278。芮醯亞胺特別具有吸引力，此乃因其堅固性質、撓性分子軌道能量學及極佳電荷傳輸性質。然而，包括PDI-FCN₂及NDI-F在內之高遷移率芮化合物溶解度差。另一方面，可溶性芮化合物通常具有弱電荷傳輸性質。The most common air-stable n-type organic semiconductors include perfluorinated copper phthalocyanine (CuF ₁₆ Pc), fluorononyl oligothiophene (eg, DFCO-4TCO), N,N'-fluorocarbon substituted naphthalene diterpenes An imine (eg, NDI-F, NDI-XF), a cyano substituted indole diimide (eg, PDI-FCN ₂ ), and a cyano substituted naphthalene diimine (eg, NDI-8CN ₂ ). See, for example, Bao et al. (1998), J. Am. Chem. Soc, 120: 207-208; de Oteyza et al. (2005), Appl. Phys. Lett., 87: 183504; Schon et al. (2000) , Adv Mater . 12: 1539-1542; Ye et al. (2005), Appl. Phys. Lett., 86: 253505; Yoon et al. (2006), J. Am. Chem. Soc, 128: 12851-12869; Tong Et al. (2006), J. Phys. Chem. B., 110: 17406-17413; Yuan et al. (2004), Thin Solid Films, 450: 316-319; Yoon et al. (2005), J. Am. Chem Soc, 127: 1348-1349; Katz et al. (2000), J. Am. Chem. Soc, 122: 7787-7792; Katz et al. (2000), Nature (London), 404: 478-481; Katz et al. Human (2001), Chem. Phys. Chem., 3: 167-172; Jung et al. (2006), Appl. Phys. Lett., 88: 183102; Yoo et al. (2006), IEEE Electron Device Lett., 27 : 737-739; Jones et al. (2004), Angew. Chem., Int. Ed. Engl., 43: 6363-6366; and Jones et al. (2007), J. Am. Chem. Soc, 129: 15259- 15278. Bismumine is particularly attractive due to its robust nature, flexible molecular orbital energetics, and excellent charge transport properties. However, high mobility ruthenium compounds including PDI-FCN ₂ and NDI-F have poor solubility. On the other hand, soluble hydrazine compounds generally have weak charge transport properties.

因此，倘若可能應用於可藉由高通量卷軸至卷軸製造法製造之便宜的大面積有機電子裝置中，則該項技術需要新的有機n-型半導電化合物，尤其彼等具有諸如下列等合意性質者：空氣穩定性、高電荷傳輸效率及在常見溶劑中之良好溶解度。Therefore, if it is possible to apply to inexpensive large-area organic electronic devices that can be manufactured by high-throughput reel-to-reel manufacturing methods, the technology requires new organic n-type semi-conductive compounds, especially such as the following. Desirable properties: air stability, high charge transport efficiency, and good solubility in common solvents.

根據上文所述，本發明之目的係提供可用作有機半導體之化合物及相關材料、組合物、複合物及/或裝置，該等可克服包括彼等上文所概述者在內之先前技術之各種不足及缺點。In light of the foregoing, it is an object of the present invention to provide compounds and related materials, compositions, composites and/or devices useful as organic semiconductors that overcome the prior art including those outlined above. Various shortcomings and shortcomings.

更特定而言，本發明提供具有半導電活性之經氰硫基取代之萘二醯亞胺及芮二醯亞胺化合物及衍生物。自此等化合物製備之材料已展現意想不到的性質及結果。舉例而言，已發現，當與相關代表性化合物相比時，本發明之化合物在場效應裝置(例如，薄膜電晶體)中可具有更高載流子遷移率及/或更佳電流調變特性。另外，已經發現，與相關代表性化合物相比，本發明之化合物可具有諸如利於溶液處理之更佳溶解度及/或在環境條件下之良好穩定性(例如，空氣穩定性)等某些處理優勢。此外，該等化合物可嵌入其他組份中以用於各種基於半導體之裝置。More particularly, the present invention provides thiocyanate substituted naphthalene diimine and quinone diimine compounds and derivatives having semiconducting activity. Materials prepared from such compounds have exhibited unexpected properties and results. For example, it has been discovered that compounds of the invention may have higher carrier mobility and/or better current modulation in field effect devices (eg, thin film transistors) when compared to related representative compounds. characteristic. Additionally, it has been discovered that the compounds of the present invention may have certain processing advantages such as better solubility for solution processing and/or good stability under ambient conditions (e.g., air stability) as compared to related representative compounds. . In addition, the compounds can be embedded in other components for use in a variety of semiconductor-based devices.

該問題係藉由式I化合物來解決：This problem is solved by a compound of formula I:

其中：R¹及R²在每次出現時獨立地選自H、C_1-30烷基、C_2-30烯基、C_2-30炔基、C_1-30鹵烷基及3至22員環狀部分，其各自視情況經1個至4個獨立地選自下列之基團取代：鹵素、-CN、-NO₂、-C(O)H、-C(O)OH、-CONH₂、-OH、-NH₂、-CO(C_1-10烷基)、-C(O)OC_1-14烷基、-CONH(C_1-14烷基)、-CON(C_1-14烷基)₂、-S-C_1-14烷基、-O-(CH₂CH₂O)_n(C_1-14烷基)、-NH(C_1-14烷基)、-N(C_1-14烷基)₂、C_1-14烷基、C_2-14烯基、C_2-14炔基、C_1-14鹵烷基、C_1-14烷氧基、C_6-14芳基、C_3-14環烷基、3至14員雜環烷基及5至14員雜芳基；R³獨立地選自鹵素-、CN、-NO₂、-C(O)O(C_1-14烷基)、-C(O)O(C_6-14芳基)、-CHO、C_1-14烷基碸基、C_6-14芳基碸基、磺酸C_1-14烷基酯基或C_6-14芳基酯基、-CONH₂、-CONH(C_1-14烷基)、-CONH(C_6-14芳基)、-CON(C_1-14烷基)₂、-CON(C_1-14烷基)(C_6-14芳基)、-CON(C_6-14芳基)₂、-C(O)H、C_1-14烷氧基、C_1-14烷硫基、C_6-14芳氧基、C_6-14芳硫基、C_1-14烷基、3至14員雜環烷基、C_6-20芳基及5至20員雜芳基；及n係0、1、2或3；若n>0，則x係0、1、2、3或4；若z係0，則y係1、2、3或4，且若z>0，則y係0、1、2、3或4；若y係0，則z係1、2、3或4，且若y>0，則z係0、1、2、3或4。Wherein: R ¹ and R ² are independently selected from H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _1-30 haloalkyl and 3 to 22 at each occurrence. The cyclic moiety, each of which is optionally substituted with one to four groups independently selected from the group consisting of halogen, -CN, -NO ₂ , -C(O)H, -C(O)OH, -CONH ₂ , -OH, -NH ₂ , -CO(C _1-10 alkyl), -C(O)OC _1-14 alkyl, -CONH(C _1-14 alkyl), -CON(C _1-14 Alkyl) ₂ , -SC _1-14 alkyl, -O-(CH ₂ CH ₂ O) _n (C _1-14 alkyl), -NH(C _1-14 alkyl), -N (C _{1- 14} alkyl) ₂ , C _1-14 alkyl, C _2-14 alkenyl, C _2-14 alkynyl, C _1-14 haloalkyl, C _1-14 alkoxy, C _6-14 aryl, C _3-14 cycloalkyl, 3 to 14 membered heterocycloalkyl and 5 to 14 membered heteroaryl; R ^{3 is} independently selected from halogen -, CN, -NO ₂ , -C(O)O (C _{1- 14} alkyl), -C(O)O(C _6-14 aryl), -CHO, C _1-14 alkyl fluorenyl, C _6-14 aryl fluorenyl, sulfonic acid C _1-14 alkyl ester Or a C _6-14 aryl ester group, -CONH ₂ , -CONH(C _1-14 alkyl), -CONH(C _6-14 aryl), -CON(C _1-14 alkyl) ₂ ,- CON(C _1-14 alkyl)(C _6-14 aryl), -CON(C _6-14 aryl) ₂ , -C(O)H, C _1-14 alkoxy, C _1-14 alkane Sulfur-based, C _6-14 aromatic Oxyl, C _6-14 arylthio, C _1-14 alkyl, 3 to 14 membered heterocycloalkyl, C _6-20 aryl and 5 to 20 membered heteroaryl; and n series 0, 1, 2 Or 3; if n>0, x is 0, 1, 2, 3 or 4; if z is 0, then y is 1, 2, 3 or 4, and if z>0, then y is 0, 1, 2, 3 or 4; if y is 0, then z is 1, 2, 3 or 4, and if y > 0, then z is 0, 1, 2, 3 or 4.

本發明亦提供製備此等化合物及半導體材料之方法以及納入本文所揭示化合物及半導體材料之各種組合物、複合物及裝置。The present invention also provides methods of making such compounds and semiconductor materials, as well as various compositions, composites, and devices incorporating the compounds and semiconductor materials disclosed herein.

自下文圖、實施方式及申請專利範圍可更全面地理解本發明之上述以及其他特徵及優點。The above as well as other features and advantages of the present invention will be more fully understood from the appended claims appended claims.

在整個實施方式中，當將組合物闡述為具有、包括或包含特定組份或當將製程闡述為具有、包括或包含特定製程步驟時，預計本發明組合物亦可基本上由所述及組份組成或由其組成且本發明製程亦可基本上由所述及製程步驟組成或由其組成。In the entire embodiment, when the composition is described as having, including or comprising a particular component or when the process is described as having, including or comprising a particular process step, it is contemplated that the composition of the invention may also consist essentially of the group The composition of or consists of and the process of the invention may consist essentially of or consist of the process steps described.

在本申請案中，當成份或組份被描述為包括於及/或選自所述及成份或組份列表時，應理解，該成份或組份可為所述及成份或組份中之任一者且可選自由兩種或更多種所述及成份或組份組成之群。此外，應理解本文所述組合物、設備或方法之成份及/或特徵在不背離本發明之精神及範疇的情況下可以各種方式組合，無論本文直接抑或間接說明。In the present application, when a component or component is described as being included in and/or selected from the list of ingredients and components, it is understood that the component or component may be in the component or component. Either and optionally a group of two or more of said ingredients or components can be selected. In addition, it is to be understood that the components and/or features of the compositions, devices, or methods described herein may be combined in various ways, whether directly or indirectly, without departing from the spirit and scope of the invention.

除非另有明確說明，否則所用術語「包括(include,includes,including)」、「具有(have、has或having)」通常應理解為具有廣義含義且不具限制性。The terms "include, includes," and "have," or "having" are generally understood to have a broad meaning and are not limiting.

除非另有明確說明，否則本文所用單數形式包括複數形式(且反之亦然)。The singular forms used herein include the plural (and vice versa) unless specifically stated otherwise.

本文所用「鹵基」或「鹵素」係指氟、氯、溴及碘。As used herein, "halo" or "halogen" means fluoro, chloro, bromo and iodo.

本文所用「烷氧基」係指-O-烷基。烷氧基之實例包括但不限於甲氧基、乙氧基、丙氧基(例如，正丙氧基及異丙氧基)、第三丁氧基及諸如此類。-O-烷基中之烷基可如本文所述經取代。As used herein, "alkoxy" refers to -O-alkyl. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy (eg, n-propoxy and isopropoxy), tert-butoxy, and the like. The alkyl group in the -O-alkyl group can be substituted as described herein.

本文所用「烷硫基」係指-S-烷基。烷硫基之實例包括但不限於甲硫基、乙硫基、丙硫基(例如，正丙硫基及異丙硫基)、第三丁硫基及諸如此類。-S-烷基中之烷基可如本文所述經取代。As used herein, "alkylthio" refers to -S-alkyl. Examples of alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio (eg, n-propylthio and isopropylthio), tert-butylthio, and the like. The alkyl group in the -S-alkyl group can be substituted as described herein.

本文所用「酮基」係指雙鍵氧(即，=O)。As used herein, "keto" refers to double bond oxygen (ie, =O).

R¹、R²可為C_1-30烷基。本文所用「烷基」係指直鏈或具支鏈飽和烴基。烷基之實例包括甲基(Me)、乙基(Et)、丙基(例如，正丙基及異丙基)、丁基(例如，正丁基、異丁基、第二丁基、第三丁基)、戊基(例如，正戊基、異戊基、新戊基)及諸如此類。烷基可具有1個至30個碳原子，例如，1個至20個碳原子(即，C_1-20烷基)。低碳數烷基通常具有至多4個碳原子。低碳數烷基之實例包括甲基、乙基、丙基(例如，正丙基及異丙基)及丁基(例如，正丁基、異丁基、第二丁基、第三丁基)。在一些實施例中，烷基可如本文所揭示經取代。R ¹ and R ² may be a C _1-30 alkyl group. As used herein, "alkyl" refers to a straight or branched saturated hydrocarbon group. Examples of the alkyl group include methyl (Me), ethyl (Et), propyl (for example, n-propyl and isopropyl), butyl (for example, n-butyl, isobutyl, t-butyl, Tributyl), pentyl (eg, n-pentyl, isopentyl, neopentyl) and the like. The alkyl group may have from 1 to 30 carbon atoms, for example, from 1 to 20 carbon atoms (i.e., C _1-20 alkyl). Lower alkyl groups typically have up to 4 carbon atoms. Examples of lower alkyl groups include methyl, ethyl, propyl (for example, n-propyl and isopropyl) and butyl (for example, n-butyl, isobutyl, t-butyl, t-butyl) ). In some embodiments, an alkyl group can be substituted as disclosed herein.

R¹、R²可為C_1-30鹵烷基。本文所用「鹵烷基」係指具有一或多個鹵素取代基之烷基。鹵烷基可具有1個至30個碳原子，例如，1個至10個碳原子(即，C_1-10鹵烷基)。鹵烷基之例包括CF₃、C₂F₅、CHF₂、CH₂F、CCl₃、CHCl₂、CH₂Cl、C₂Cl₅及諸如此類。全鹵烷基，即，所有氫原子均由鹵素原子代替之烷基(例如，CF₃及C₂F₅)屬於「鹵烷基」之定義。舉例而言，C_1-20鹵烷基可具有式-C_aE_2a+1-bX_b，其中X在每次出現時係F、Cl、Br或I，a係在1至20範圍內之整數，且b係在1至41範圍內之整數，條件係b不大於2a+1。R ¹ and R ² may be a C _1-30 haloalkyl group. As used herein, "haloalkyl" refers to an alkyl group having one or more halo substituents. The haloalkyl group may have 1 to 30 carbon atoms, for example, 1 to 10 carbon atoms (i.e., a C _1-10 haloalkyl group). Examples of haloalkyl groups include CF ₃ , C ₂ F ₅ , CHF ₂ , CH ₂ F, CCl ₃ , CHCl ₂ , CH ₂ Cl, C ₂ Cl ₅ and the like. A perhaloalkyl group, that is, an alkyl group in which all hydrogen atoms are replaced by a halogen atom (for example, CF ₃ and C ₂ F ₅ ) is defined as a "haloalkyl group". For example, a C _1-20 haloalkyl group can have the formula -C _a E _2a+1-b X _b , wherein X is F, Cl, Br or I at each occurrence, and a is in the range of 1 to 20 An integer, and b is an integer in the range of 1 to 41, and the condition is b not greater than 2a+1.

R¹、R²可為C_2-30烯基。本文所用「烯基」係指具有一或多個碳-碳雙鍵之直鏈或具支鏈烷基。在各實施例中，烯基可具有2個至30個碳原子，例如，2個至10個碳原子(即，C_2-10烯基)。烯基之實例包括但不限於乙烯基、丙烯基、丁烯基、戊烯基、己烯基、丁二烯基、戊二烯基、己二烯基及諸如此類。該一或多個碳碳雙鍵可為內鍵(例如在2-丁烯中)或端鍵(例如在1-丁烯中)。在一些實施例中，烯基可如本文所揭示經取代。R ¹ and R ² may be a C _2-30 alkenyl group. As used herein, "alkenyl" refers to a straight or branched alkyl group having one or more carbon-carbon double bonds. In various embodiments, an alkenyl group can have from 2 to 30 carbon atoms, for example, from 2 to 10 carbon atoms (ie, a C _2-10 alkenyl group). Examples of alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, and the like. The one or more carbon-carbon double bonds may be internal bonds (for example in 2-butene) or terminal bonds (for example in 1-butene). In some embodiments, an alkenyl group can be substituted as disclosed herein.

R¹、R²可為C_2-30炔基。本文所用「炔基」係指具有一或多個碳-碳三鍵之直鏈或具支鏈烷基。炔基之實例包括乙炔基、丙炔基、丁炔基、戊炔基及諸如此類。該一或多個碳碳三鍵可為內鍵(例如在2-丁炔中)或端鍵(例如在1-丁炔中)。在各實施例中，炔基可具有2個至30個碳原子，例如，2個至10個碳原子(即，C_2-10炔基)。在一些實施例中，炔基可如本文所揭示經取代。R ¹ and R ² may be a C _2-30 alkynyl group. As used herein, "alkynyl" refers to a straight or branched alkyl group having one or more carbon-carbon triple bonds. Examples of alkynyl groups include ethynyl, propynyl, butynyl, pentynyl and the like. The one or more carbon-carbon triple bonds can be internal bonds (eg, in 2-butyne) or end bonds (eg, in 1-butyne). In various embodiments, an alkynyl group can have from 2 to 30 carbon atoms, for example, from 2 to 10 carbon atoms (ie, a C _2-10 alkynyl group). In some embodiments, an alkynyl group can be substituted as disclosed herein.

R¹、R²可為3至22員環狀部分。本文所用「環狀部分」可包括一或多個(例如，1個至6個)碳環或雜環。該環狀部分可為環烷基、雜環烷基、芳基或雜芳基(即，可僅包括飽和鍵，或可包括一或多個不飽和鍵，與芳香性無關)，其各自包括(例如)3個至22個環原子且可視情況如本文所述經取代。在環狀部分係「單環部分」之一些實施例中，該「單環部分」可包括3至14員芳香族或非芳香族碳環或雜環。單環部分可包括(例如)苯基或5或6員雜芳基，其各自可視情況如本文所述經取代。在環狀部分係多環部分之一些實施例中，該多環部分可包括兩個或更多個經由單鍵或螺原子、或一或多個橋接原子彼此稠合或彼此連接之環。多環部分可包括8至22員芳香族或非芳香族、碳環或雜環，例如C_8-22芳基或8至22員雜芳基，其各自可視情況如本文所述經取代。R ¹ and R ² may be a 3 to 22 member cyclic portion. As used herein, "cyclic moiety" may include one or more (eg, 1 to 6) carbocyclic or heterocyclic rings. The cyclic moiety can be a cycloalkyl, heterocycloalkyl, aryl or heteroaryl group (ie, can include only saturated bonds, or can include one or more unsaturated bonds, independent of aromaticity), each of which includes (for example) 3 to 22 ring atoms and optionally substituted as described herein. In some embodiments in which the cyclic moiety is a "monocyclic moiety", the "monocyclic moiety" may include from 3 to 14 members of an aromatic or non-aromatic carbocyclic or heterocyclic ring. Monocyclic moieties can include, for example, phenyl or 5 or 6 membered heteroaryl groups, each of which can be substituted as described herein, as appropriate. In some embodiments in which the cyclic moiety is a polycyclic moiety, the polycyclic moiety can include two or more rings that are fused to each other or to each other via a single bond or a spiro atom, or one or more bridging atoms. The polycyclic moiety can include from 8 to 22 members of an aromatic or non-aromatic, carbocyclic or heterocyclic ring, such as a _C8-22 aryl group or a 8 to 22 membered heteroaryl group, each of which can be optionally substituted as described herein.

R¹、R²可為具有3個至22個碳原子之環烷基。本文所用「環烷基」係指非芳香族碳環基團，包括環化烷基、烯基及炔基。環烷基可具有3個至22個碳原子，例如，3個至14個碳原子(即，C_3-14環烷基)。環烷基可為單環(例如，環己基)或多環(例如，含有稠合、橋接及/或螺環系統)，其中碳原子可位於環系統之內部或外部。環烷基之實例包括但不限於環丙基、環丁基、環戊基、環己基、環庚基、環戊烯基、環己烯基、環己二烯基、環庚三烯基、降莰基、降蒎烷基(norpinyl)、降蒈烷基(norcaryl)、金鋼烷基及螺[4.5]癸基以及其同系物、異構體及諸如此類。在一些實施例中，環烷基可如本文所揭示經取代。R ¹ and R ² may be a cycloalkyl group having 3 to 22 carbon atoms. As used herein, "cycloalkyl" refers to a non-aromatic carbocyclic group, including cyclized alkyl, alkenyl, and alkynyl groups. The cycloalkyl group may have 3 to 22 carbon atoms, for example, 3 to 14 carbon atoms (i.e., C _3-14 cycloalkyl). A cycloalkyl group can be a monocyclic (eg, cyclohexyl) or polycyclic (eg, containing a fused, bridged, and/or spiro ring system) in which the carbon atoms can be internal or external to the ring system. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, Lowering thiol, norpinyl, norcaryl, ruthenium alkyl and spiro[4.5] fluorenyl as well as homologs, isomers and the like. In some embodiments, a cycloalkyl group can be substituted as disclosed herein.

本文所用「雜原子」係指除碳或氫外之任一元素的原子且包括(例如)氮、氧、矽、硫、磷及硒。As used herein, "heteroatom" refers to an atom of any element other than carbon or hydrogen and includes, for example, nitrogen, oxygen, helium, sulfur, phosphorus, and selenium.

R¹、R²可為具有3個至22個環原子之雜環烷基。本文所用「雜環烷基」係指含有至少一個選自O、S、Se、N、P及Si(例如，O、S及N)且視情況含有一或多個雙鍵或三鍵之非芳香族環烷基。雜環烷基可具有3個至22個環原子，例如，3個至14個環原子(即，3至14員雜環烷基)。雜環烷基環中之一或多個N、P、S或Se原子(例如，N或S)可經氧化(例如，嗎啉N-氧化物、硫嗎啉S-氧化物、硫嗎啉S,S-二氧化物)。在一些實施例中，雜環烷基之氮或磷原子可具有取代基，例如，氫原子、烷基、或如本文所述其他取代基。雜環烷基亦可含有一或多個側氧基，例如側氧基六氫吡啶基、側氧基噁唑啶基、二側氧基-(1H,3H)-嘧啶基、側氧基-2(1H)-吡啶基及諸如此類。雜環烷基之實例尤其包括嗎啉基、硫嗎啉基、哌喃基、咪唑啶基、咪唑啉基、噁唑啶基、吡唑啶基、吡唑啉基、吡咯啶基、吡咯啉基、四氫呋喃基、四氫苯硫基、六氫吡啶基、六氫吡嗪基及諸如此類。在一些實施例中，雜環烷基可如本文所揭示經取代。R ¹ and R ² may be a heterocycloalkyl group having 3 to 22 ring atoms. As used herein, "heterocycloalkyl" refers to a non-containing one or more selected from the group consisting of O, S, Se, N, P, and Si (eg, O, S, and N) and optionally one or more double or triple bonds. Aromatic cycloalkyl. Heterocycloalkyl groups can have from 3 to 22 ring atoms, for example, from 3 to 14 ring atoms (i.e., from 3 to 14 membered heterocycloalkyl). One or more N, P, S or Se atoms (eg, N or S) in the heterocycloalkyl ring can be oxidized (eg, morpholine N-oxide, thiomorpholine S-oxide, thiomorpholine) S, S-dioxide). In some embodiments, the nitrogen or phosphorus atom of the heterocycloalkyl group can have a substituent, for example, a hydrogen atom, an alkyl group, or other substituents as described herein. Heterocycloalkyl can also contain one or more pendant oxy groups, such as pendant hexahydropyridinyl, oxoxazolidinyl, di-oxy-(1H,3H)-pyrimidinyl, pendant oxy- 2(1H)-pyridyl and the like. Examples of heterocycloalkyl groups include, in particular, morpholinyl, thiomorpholinyl, piperidyl, imidazolidinyl, imidazolinyl, oxazolidinyl, pyrazolyl, pyrazolinyl, pyrrolidinyl, pyrroline Base, tetrahydrofuranyl, tetrahydrophenylthio, hexahydropyridyl, hexahydropyrazinyl and the like. In some embodiments, a heterocycloalkyl group can be substituted as disclosed herein.

R¹、R²可為具有6個至22個環原子之芳基。本文所用「芳基」係指兩個或更多個芳香族烴環稠合(即，共有一個鍵)在一起或至少一個芳香族單環烴環與一或多個環烷基及/或雜環烷基環稠合之芳香族烴單環環系統或多環環系統。芳基在其環系統中可具有6個至22個環原子，例如，6個至14個環原子(即，C_6-14芳基)，其可包括多個稠環。在一些實施例中，多環芳基可具有8個至22個碳原子。芳基之任一適宜環位置可與指定化學結構共價連接。僅具有芳香族碳環之芳基的實例包括但不限於苯基、1-萘基(二環)、2-萘基(二環)、蒽基(三環)、菲基(三環)及類似基團。至少一個芳香族碳環與一或多個環烷基及/或雜環烷基環稠合之多環環系統的實例尤其包括環戊烷之苯并衍生物(即，二氫茚基，其係5,6-二環環烷基/芳香族環系統)、環己烷之苯并衍生物(即，四氫萘基，其係6,6-二環環烷基/芳香族環系統)、咪唑啉之苯并衍生物(即，苯并咪唑啉基，其係5,6-二環雜環烷基/芳香族環系統)及哌喃之苯并衍生物(即，苯并哌喃基，其係6,6-二環雜環烷基/芳香族環系統)。芳基之其他實例包括但不限於苯并二噁烷基、苯并間二氧雜環戊烯基、基、二氫吲哚基及諸如此類。在一些實施例中，芳基可如本文所揭示經取代。在一些實施例中，芳基可具有一或多個鹵素取代基且可稱作「鹵芳基」基團。全鹵芳基，即，所有氫原子均由鹵素原子替代之芳基(例如，-C₆F₅)，係包括於「鹵芳基」之定義內。在一些實施例中，芳基係經另一芳基取代且可稱作聯芳基。聯芳基中之每一芳基可如本文所揭示經取代。R ¹ and R ² may be an aryl group having 6 to 22 ring atoms. As used herein, "aryl" means that two or more aromatic hydrocarbon rings are fused (ie, have one bond in common) or at least one aromatic monocyclic hydrocarbon ring and one or more cycloalkyl and/or hetero A cycloalkyl ring fused aromatic hydrocarbon monocyclic ring system or a polycyclic ring system. The aryl group may have from 6 to 22 ring atoms in its ring system, for example, from 6 to 14 ring atoms (i.e., C _6-14 aryl), which may include multiple fused rings. In some embodiments, a polycyclic aryl group can have from 8 to 22 carbon atoms. Any suitable ring position of the aryl group can be covalently attached to the specified chemical structure. Examples of aryl groups having only an aromatic carbocyclic ring include, but are not limited to, phenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), fluorenyl (tricyclic), phenanthryl (tricyclic), and Similar group. Examples of polycyclic ring systems in which at least one aromatic carbocyclic ring is fused to one or more cycloalkyl and/or heterocycloalkyl rings include, in particular, benzo derivatives of cyclopentane (i.e., indoline, which a 5,6-bicyclic cycloalkyl/aromatic ring system), a benzo derivative of cyclohexane (ie, tetrahydronaphthyl, which is a 6,6-bicyclic cycloalkyl/aromatic ring system) a benzo derivative of imidazoline (ie, benzimidazolyl, which is a 5,6-bicycloheterocycloalkyl/aromatic ring system) and a benzo derivative of piperazine (ie, benzopyran) a group which is a 6,6-bicyclic heterocycloalkyl/aromatic ring system). Other examples of aryl groups include, but are not limited to, benzodioxanyl, benzodioxolyl, Base, dihydroindenyl and the like. In some embodiments, an aryl group can be substituted as disclosed herein. In some embodiments, an aryl group can have one or more halogen substituents and can be referred to as a "haloaryl" group. A perhaloaryl group, that is, an aryl group in which all hydrogen atoms are replaced by a halogen atom (for example, -C ₆ F ₅ ), is included in the definition of "haloaryl". In some embodiments, an aryl group is substituted with another aryl group and may be referred to as a biaryl group. Each aryl group in the biaryl group can be substituted as disclosed herein.

R¹、R²可為具有5個至22個環原子之雜芳基。本文所用「雜芳基」係指含有至少一個選自O、N、S、Si及Se之環雜原子的芳香族單環環系統或至少一個存於該環系統中之環係芳香族環且含有至少一個環雜原子的多環環系統。多環雜芳基包括兩個或更多個稠合在一起之雜芳基環及與一或多個芳香族碳環、非芳香族碳環及/或非芳香族雜環烷基環稠合之單環雜芳基環。雜芳基整體可具有5個至22個環原子(例如，5至14員雜芳基)且含有1個至5個環雜原子。該雜芳基可在會產生穩定結構之任一雜原子或碳原子處與指定化學結構附接。一般而言，雜芳基環不含O-O、S-S或S_-O鍵。然而，雜芳基中之一或多個N或S原子可經氧化(例如，吡啶N-氧化物、噻吩S-氧化物、噻吩S,S-二氧化物)。雜芳基之實例包括(例如)下文所示5或6員單環及5-6二環環系統：R ¹ and R ² may be a heteroaryl group having 5 to 22 ring atoms. As used herein, "heteroaryl" refers to an aromatic monocyclic ring system containing at least one ring heteroatom selected from O, N, S, Si, and Se or at least one cyclic aromatic ring present in the ring system. A polycyclic ring system containing at least one ring heteroatom. Polycyclic heteroaryl groups include two or more heteroaryl rings fused together and fused to one or more aromatic carbocyclic, non-aromatic carbocyclic and/or non-aromatic heterocycloalkyl rings Monocyclic heteroaryl ring. The heteroaryl group may have from 5 to 22 ring atoms in total (for example, 5 to 14 membered heteroaryl groups) and contains from 1 to 5 ring hetero atoms. The heteroaryl group can be attached to a specified chemical structure at any heteroatom or carbon atom that will result in a stable structure. In general, heteroaryl rings do not contain OO, SS or S _- O bonds. However, one or more of the N or S atoms in the heteroaryl group can be oxidized (eg, pyridine N-oxide, thiophene S-oxide, thiophene S, S-dioxide). Examples of heteroaryl groups include, for example, the 5 or 6 membered monocyclic and 5-6 bicyclic ring systems shown below:

其中T係O、S、NH、N-烷基、N-芳基、N-(芳基烷基)(例如，N-苄基)、SiH₂、SiH-(烷基)、Si(烷基)₂、SiH-(芳基烷基)、Si-(芳基烷基)₂或Si(烷基)(芳基烷基)。雜芳基之實例包括吡咯基、呋喃基、噻吩基、吡啶基、嘧啶基、嗒嗪基、吡嗪基、***基、四唑基、吡唑基、咪唑基、異噻唑基、噻唑基、噻二唑基、異噁唑基、噁唑基、噁二唑基、吲哚基、異吲哚基、苯并呋喃基、苯并噻吩基、喹啉基、2-甲基喹啉基、異喹啉基、喹喏啉基、喹唑啉基、苯并***基、苯并咪唑基、苯并噻唑基、苯并異噻唑基、苯并異噁唑基、苯并噁二唑基、苯并噁唑基、啉基、1H-吲唑基、2H-吲唑基、吲嗪基、異苯并呋喃基、萘啶基、呔嗪基、喋啶基、嘌呤基、噁唑并吡啶基、噻唑并吡啶基、咪唑并吡啶基、呋喃并吡啶基、噻吩并吡啶基、吡啶并嘧啶基、吡啶并吡嗪基、吡啶并嗒嗪基、噻吩并噻唑基、噻吩并噁唑基、噻吩并咪唑基及諸如此類。雜芳基之其他實例包括但不限於4,5,6,7-四氫吲哚基、四氫喹啉基、苯并噻吩并吡啶基、苯并呋喃并吡啶基及諸如此類。在一些實施例中，雜芳基可如本文所揭示經取代。Wherein T is O, S, NH, N-alkyl, N-aryl, N-(arylalkyl) (eg, N-benzyl), SiH ₂ , SiH-(alkyl), Si (alkyl ₂ ) SiH-(arylalkyl), Si-(arylalkyl) ₂ or Si(alkyl)(arylalkyl). Examples of heteroaryl groups include pyrrolyl, furyl, thienyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl , thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, fluorenyl, isodecyl, benzofuranyl, benzothienyl, quinolyl, 2-methylquinolinyl , isoquinolinyl, quinoxalinyl, quinazolinyl, benzotriazolyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazole Base, benzoxazolyl, Lolinyl, 1H-carbazolyl, 2H-carbazolyl, pyridazinyl, isobenzofuranyl, naphthyridinyl, pyridazinyl, acridinyl, indolyl, oxazolopyridinyl, thiazolopyridinyl , imidazopyridyl, furopyridinyl, thienopyridyl, pyridopyrimidinyl, pyridopyrazinyl, pyridopyridazinyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, and the like . Other examples of heteroaryl groups include, but are not limited to, 4,5,6,7-tetrahydroindenyl, tetrahydroquinolyl, benzothienopyridinyl, benzofuropyridinyl, and the like. In some embodiments, a heteroaryl group can be substituted as disclosed herein.

本發明之化合物可包括在本文中定義為與兩個其他部分能夠形成共價鍵之連接基團的「二價基團」。舉例而言，本發明之化合物可包括二價C_1-20烷基，例如，亞甲基。The compounds of the present invention may include a "divalent group" as defined herein as a linking group capable of forming a covalent bond with two other moieties. For example, a compound of the invention may include a divalent C _1-20 alkyl group, for example, a methylene group.

在本說明書之各處，分組或分範圍揭示化合物之取代基。該實施方式意欲具體包括該等組及範圍之成員的每一個單獨子組合。舉例而言，術語「C_1-6烷基」意欲具體單獨揭示C₁、C₂、C₃、C₄、C₅、C₆、C₁-C₆、C₁-C₅、C₁-C₄、C₁-C₃、C₁-C₂、C₂-C₆、C₂-C₅、C₂-C₄、C₂-C₃、C₃-C₆、C₃-C₅、C₃-C₄、C₄-C₆、C₄-C₅及C₅-C₆烷基。另外舉例而言，在0至40範圍內之整數意欲具體單獨揭示0、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39及40，且在1至20範圍內之整數意欲具體單獨揭示1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19及20。額外實例包括短語「視情況經1個至5個取代基取代」意欲具體單獨揭示可包括0個、1個、2個、3個、4個、5個、0個至5個、0個至4個、0個至3個、0個至2個、0個至1個、1個至5個、1個至4個、1個至3個、1個至2個、2個至5個、2個至4個、2個至3個、3個至5個、3個至4個及4個至5個取代基之化學基團。Substituents of the compounds are disclosed in groups or sub-ranges throughout the specification. This embodiment is intended to specifically encompass each individual subcombination of the members of the group and scope. For example, the term "C _1-6 alkyl" is intended to specifically disclose C ₁ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₁ -C ₆ , C ₁ -C ₅ , C ₁ - C ₄ , C ₁ -C ₃ , C ₁ -C ₂ , C ₂ -C ₆ , C ₂ -C ₅ , C ₂ -C ₄ , C ₂ -C ₃ , C ₃ -C ₆ , C ₃ -C ₅ C ₃ -C ₄ , C ₄ -C ₆ , C ₄ -C ₅ and C ₅ -C ₆ alkyl. By way of example, an integer in the range of 0 to 40 is intended to specifically disclose 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 and 40, and An integer in the range of 1 to 20 is intended to specifically disclose 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20. Additional examples include the phrase "optionally substituted with 1 to 5 substituents" intended to specifically disclose 0, 1, 2, 3, 4, 5, 0 to 5, 0 Up to 4, 0 to 3, 0 to 2, 0 to 1, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 5 Chemical groups of 2 to 4, 2 to 3, 3 to 5, 3 to 4 and 4 to 5 substituents.

本文所述化合物可含有不對稱原子(亦稱作對掌性中心)且一些化合物可含有兩個或更多個不對稱原子或中心，因此其可產生光學異構體(對映異構體)及非對映異構體(幾何異構體)。本發明包括該等光學異構體及非對映異構體，包括其相應的拆分對映異構或非對映異構純異構體(例如，(+)或(-)立體異構體)及其外消旋混合物、以及該等對映異構體與非對映異構體之其他混合物。在一些實施例中，光學異構體可藉由熟習此項技術者已知的標準程序以富含對映異構體之形式或純淨形式獲得，該等標準程序包括(例如)對掌性分離、非對映異構鹽或酯形成、動力學拆分、酶促拆分及不對稱合成。本發明亦涵蓋含有烯基部分(例如，烯烴及亞胺)之化合物的順式及反式異構體。亦應理解，本發明涵蓋呈純淨形式及其混合物之所有可能的區域異構體，該等區域異構體可藉助熟習此項技術者已知之標準分離程序來獲得，例如，管柱層析、薄層層析、模擬移動床層析及高效液相層析。舉例而言，本發明之苝化合物包括呈其純淨形式或其混合物之苝衍生物，其中該等苝衍生物可經1個、2個、3個、4個、5個、6個、7個或8個取代基取代。本發明之萘化合物包括呈其純淨形式或其混合物之萘衍生物，其中該等萘衍生物可經1個、2個、3個或4個取代基取代。特定而言，該等苝衍生物可包括具有如下部分之化合物：The compounds described herein may contain asymmetric atoms (also known as palmar centers) and some compounds may contain two or more asymmetric atoms or centers, such that they may produce optical isomers (enantiomers) And diastereomers (geometric isomers). The present invention includes such optical isomers and diastereomers, including the corresponding resolved enantiomerically or diastereomeric pure isomers (e.g., (+) or (-) stereoisomers. And its racemic mixture, and other mixtures of such enantiomers and diastereomers. In some embodiments, optical isomers may be obtained in enantiomerically enriched or pure form by standard procedures known to those skilled in the art, including, for example, palm separation. , diastereomeric salt or ester formation, kinetic resolution, enzymatic resolution and asymmetric synthesis. The cis and trans isomers of compounds containing alkenyl moieties (e.g., olefins and imines) are also contemplated by the present invention. It is also to be understood that the invention encompasses all possible regioisomers in pure form and mixtures thereof, which can be obtained by standard separation procedures known to those skilled in the art, for example, column chromatography, Thin layer chromatography, simulated moving bed chromatography and high performance liquid chromatography. For example, the indole compound of the present invention includes an anthracene derivative in its pure form or a mixture thereof, wherein the indole derivatives may be passed through 1, 2, 3, 4, 5, 6, 7 Or substituted with 8 substituents. The naphthalene compounds of the present invention include naphthalene derivatives in their pure form or mixtures thereof, wherein the naphthalene derivatives may be substituted with 1, 2, 3 or 4 substituents. In particular, the indole derivatives may include a compound having the following moiety:

其中Y在每次出現時可為H、氰硫基或異氰硫基。Wherein Y may be H, thiocyanyl or isothiocyanate at each occurrence.

在各實施例中，兩個Y基團係H且另兩個Y基團獨立地係氰硫基或異氰硫基。因此，在兩個Y基團係H且另兩個獨立地係氰硫基或異氰硫基之實施例中，本發明之化合物可具有具下式之立體異構體：In various embodiments, two Y groups are H and the other two Y groups are independently thiocyano or isocyanato. Thus, in embodiments where two Y groups are H and the other two are independently thiocyano or isocyanato groups, the compounds of the invention may have stereoisomers of the formula:

在某些實施例中，本發明之化合物可包括具有式i或ii之化合物：In certain embodiments, the compounds of the invention may include a compound having formula i or ii:

或其混合物，其中Y獨立地係氰硫基或異氰硫基。Or a mixture thereof, wherein Y is independently a thiocyanato or isocyanato group.

本文所用「p-型半導電材料」或「p-型半導體」係指電洞作為主要載流子之半導電材料。在一些實施例中，當將p-型半導電材料沈積於基板上時，其可提供超過約10^-5 cm²/Vs之電洞遷移率。倘若為場效應裝置，則p-型半導體亦可呈現大於約10之電流導通/關斷比。As used herein, "p-type semiconducting material" or "p-type semiconductor" refers to a semiconducting material in which a hole is a main carrier. In some embodiments, when a p-type semiconductive material is deposited on a substrate, it can provide a hole mobility in excess of about 10 ^-5 cm ² /Vs. In the case of a field effect device, the p-type semiconductor can also exhibit a current conduction/shutdown ratio greater than about 10.

本文所用「n-型半導電材料」或「n-型半導體」係指電子作為主要載流子之半導電材料。在一些實施例中，當將n-型半導電材料沈積於基板上時，其可提供超過約10^-5 cm²/Vs之電子遷移率。倘若為場效應裝置，則n-型半導體亦可呈現大於約10之電流導通/關斷比。As used herein, "n-type semiconducting material" or "n-type semiconductor" refers to a semiconducting material in which electrons are the main carriers. In some embodiments, when an n-type semiconductive material is deposited on a substrate, it can provide an electron mobility in excess of about 10 ^-5 cm ² /Vs. In the case of a field effect device, the n-type semiconductor can also exhibit a current conduction/shutdown ratio greater than about 10.

本文所用「場效應遷移率」係指電荷載流子在電場影響下移動經過材料之速度的量度，例如，倘若為p-型半導電材料，則電荷載流子為電洞(或正電荷之單元)且倘若為n-型半導電材料，則電荷載流子為電子。As used herein, "field effect mobility" refers to a measure of the rate at which charge carriers move through a material under the influence of an electric field. For example, in the case of a p-type semiconducting material, the charge carriers are holes (or positive charges). Unit) and if it is an n-type semiconducting material, the charge carriers are electrons.

本文所用當化合物之載流子遷移率或還原電位在該化合物暴露於環境條件(例如，空氣、環境溫度及濕度)一段時間後保持在約其初始量測值時，該化合物可視為「環境溫定」或「在環境條件下穩定」。舉例而言，倘若化合物在暴露於環境條件(即，空氣、濕度及溫度)達3天、5天或10天時間後該化合物之載流子遷移率或還原電位自其初始數值變化不超過20%或不超過10%，則該化合物可闡述為環境溫定。As used herein, when the compound's carrier mobility or reduction potential is maintained at about its initial measurement after exposure to environmental conditions (eg, air, ambient temperature, and humidity) for a period of time, the compound may be considered "ambient temperature." " or "steady under environmental conditions". For example, if the compound is exposed to environmental conditions (ie, air, humidity, and temperature) for a period of 3 days, 5 days, or 10 days, the carrier mobility or reduction potential of the compound does not vary from its initial value by more than 20 % or not more than 10%, the compound can be stated as ambient temperature.

本文所用「溶液可處理」係指可用於各種溶液相製程之化合物、材料或組合物，該等溶液相製程包括旋塗、印刷(例如，噴墨印刷、絲網印刷、移動印刷、凹版印刷、柔版印刷、平版印刷、微接觸印刷及微影印刷)、噴霧、電噴霧塗佈、滴注、區域澆注、浸塗及刮塗。As used herein, "solution treatable" means a compound, material or composition that can be used in various solution phase processes, including spin coating, printing (eg, inkjet printing, screen printing, mobile printing, gravure printing, Flexographic, lithographic, microcontact printing and lithography), spray, electrospray coating, drip, zone casting, dip coating and knife coating.

在本申請案之各處，揭示溫度之範圍。該實施方式意欲具體包括在該等範圍內之更窄溫度範圍以及包含該溫度範圍之最大溫度及最小溫度。The scope of the temperature is disclosed throughout the application. This embodiment is intended to specifically include a narrower temperature range within the ranges and a maximum temperature and minimum temperature including the temperature range.

在整個說明書中，結構可用化學名稱或可不用化學名稱表示。在因命名法而產生任何疑問時，應以結構為准。Throughout the specification, the structure may be represented by a chemical name or may not be represented by a chemical name. In the event of any doubt arising from the nomenclature, the structure shall prevail.

在一個態樣中，本發明提供具有式Ia、Ib或Ic之化合物：In one aspect, the invention provides a compound having Formula Ia, Ib or Ic:

其中：R¹及R²係如上文所定義。Wherein: R ¹ and R ² are as defined above.

在又一態樣中，本發明提供具有式Id、Ie或If之化合物：In yet another aspect, the invention provides a compound having the formula Id, Ie or If:

其中R¹、R²係如上文所定義。Wherein R ¹ and R ² are as defined above.

R¹及R²在每次出現時獨立地選自H、C_1-30烷基、C_2-30烯基、C_2-30炔基、C_1-30鹵烷基及3至22員環狀部分，其各自視情況經1個至4個獨立地選自下列之基團取代：鹵素、-CN、-NO₂、-C(O)H、-C(O)OH、-CONH₂、-OH、-NH₂、-CO(C_1-14烷基)、-C(O)OC_1-14烷基、-CONH(C_1-14烷基)、-CON(C_1-14烷基)₂、-S-C_1-14烷基、-O-(CH₂CH₂O)_n(C_1-14烷基)、-NH(C_1-14烷基)、-N(C_1-14烷基)₂、C_1-14烷基、C_2-14烯基、C_2-14炔基、C_1-14鹵烷基、C_1-14烷氧基、C_6-14芳基、C_3-14環烷基、3至14員雜環烷基及5至14員雜芳基，且n係如本文所述；3至22員環狀部分可選自C_6-22芳基、5至22員雜芳基、C_3-22環烷基及3至22員雜環烷基，其各自可視情況如本文所述經取代。R ¹ and R ² are independently selected from H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _1-30 haloalkyl and 3 to 22 membered rings at each occurrence. a moiety, each of which is optionally substituted with one to four groups independently selected from the group consisting of halogen, -CN, -NO ₂ , -C(O)H, -C(O)OH, -CONH ₂ , -OH, -NH ₂ , -CO(C _1-14 alkyl), -C(O)OC _1-14 alkyl, -CONH(C _1-14 alkyl), -CON(C _1-14 alkyl ₂ , -SC _1-14 alkyl, -O-(CH ₂ CH ₂ O) _n (C _1-14 alkyl), -NH(C _1-14 alkyl), -N (C _1-14 alkane) ₂ ), C _1-14 alkyl, C _2-14 alkenyl, C _2-14 alkynyl, C _1-14 haloalkyl, C _1-14 alkoxy, C _6-14 aryl, C _{3 a -14} cycloalkyl group, a 3 to 14 membered heterocycloalkyl group, and a 5 to 14 membered heteroaryl group, and n is as described herein; a 3 to 22 membered cyclic moiety may be selected from a C _6-22 aryl group, 5 to 22-membered heteroaryl, C _3-22 cycloalkyl, and 3 to 22 membered heterocycloalkyl, each of which may be substituted as described herein, as appropriate.

在較佳實施例中，R¹及R²在每次出現時獨立地選自C_1-12烷基、C_1-12鹵烷基及5至14員單環部分，其各自視情況經1個至4個獨立地選自下列之基團取代：鹵素、-CN、-NO₂、-C(O)H、-C(O)OH、-CONH₂、-OH、-NH₂、-CO(C_1-14烷基)、-C(O)OC_1-14烷基、-CONH(C_1-14烷基)、-CON(C_1-14烷基)₂、-S-C_1-14烷基、-O-(CH₂CH₂O)_n(C_1-14烷基)、-NH(C_1-14烷基)、-N(C_1-14烷基)₂、C_1-14烷基、C_2-14烯基、C_2-14炔基、C_1-14鹵烷基、C_1-14烷氧基、C_6-14芳基、C_3-14環烷基、3至14員雜環烷基及5至14員雜芳基，且n係1、2或3。In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C _1-12 alkyl, C _1-12 haloalkyl, and 5 to 14 membered monocyclic moieties, each of which is optionally 1 One to four groups independently selected from the group consisting of halogen, -CN, -NO ₂ , -C(O)H, -C(O)OH, -CONH ₂ , -OH, -NH ₂ , -CO (C _1-14 alkyl), -C(O)OC _1-14 alkyl, -CONH(C _1-14 alkyl), -CON(C _1-14 alkyl) ₂ , -SC _1-14 alkane , -O-(CH ₂ CH ₂ O) _n (C _1-14 alkyl), -NH(C _1-14 alkyl), -N(C _1-14 alkyl) ₂ , C _1-14 alkane , C _2-14 alkenyl, C _2-14 alkynyl, C _1-14 haloalkyl, C _1-14 alkoxy, C _6-14 aryl, C _3-14 cycloalkyl, 3 to 14 Heterocycloalkyl and 5 to 14 membered heteroaryl, and n is 1, 2 or 3.

particular在具體實施例中，R¹及R²在每次出現時獨立地選自C_1-12烷基、C_1-12鹵烷基、C_7-20芳基烷基及苯基，其中苯基視情況經1個至4個獨立地選自鹵素、C_1-6烷基及C_1-6鹵烷基之基團取代。舉例而言，R¹及R²在每次出現時選自-CH₃、-C₂H₅、-C₃H₇、-C₄H₉、-C₅H₁₁、-C₆H₁₃、-C₈H₁₇(具體而言2-乙基己基)、-C₁₂H₂₅、-C₁₃H₂₇、視情況經1個至5個鹵基或C_1-6烷基取代之苯基、C_7-12苯基烷基(其中苯基視情況經1個至5個鹵基(具體而言F原子)或C_1-6烷基取代)及C_1-6鹵烷基。In particular embodiments, R ¹ and R ² are each independently selected from C _1-12 alkyl, C _1-12 haloalkyl, C _7-20 arylalkyl, and phenyl, wherein phenyl, The base-view case is substituted with 1 to 4 groups independently selected from the group consisting of halogen, C _1-6 alkyl and C _1-6 haloalkyl. For example, R ¹ and R ² are each selected from -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , -C ₅ H ₁₁ , -C ₆ H ₁₃ , -C ₈ H ₁₇ (specifically 2-ethylhexyl), -C ₁₂ H ₂₅ , -C ₁₃ H ₂₇ , optionally substituted by 1 to 5 halo or C _1-6 alkyl, C _7-12 phenylalkyl (wherein the phenyl group is optionally substituted by 1 to 5 halo groups (specifically F atoms) or C _1-6 alkyl) and C _1-6 haloalkyl.

具體鹵烷基之實例係-CF₃、-C₂F₅、-C₃F₇及-CH₂C₃F₇。具體芳基烷基之實例係苄基、苯基乙基及苯基丙基。Examples of specific haloalkyl groups are -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ and -CH ₂ C ₃ F ₇ . Examples of specific arylalkyl groups are benzyl, phenylethyl and phenylpropyl.

在各實施例中，R³係吸電子基團，其獨立地選自鹵素、-CN、-NO₂、-CF₃、-OCF₃、-CO₂(C_1-10烷基)、-CHO、C₁-C₁₄烷基碸基、C_6-14芳基碸基、磺酸-C_1-14烷基酯基或-C_6-14芳基酯基、-CONH(C_1-10烷基)、-CON(C_1-10烷基)₂。舉例而言，R³可為鹵素、-CN、-NO₂、-CF₃或-OCF₃。In various embodiments, the R ³ is an electron withdrawing group independently selected from the group consisting of halogen, —CN, —NO ₂ , —CF ₃ , —OCF ₃ , —CO ₂ (C _1-10 alkyl), —CHO , C ₁ -C ₁₄ alkyl fluorenyl, C _6-14 aryl fluorenyl, sulfonic acid-C _1-14 alkyl ester or -C _6-14 aryl ester, -CONH (C _1-10 alkane Base), -CON(C _1-10 alkyl) ₂ . For example, R ³ can be halogen, -CN, -NO ₂ , -CF ₃ or -OCF ₃ .

在某些實施例中，R³係F、CI、Br、I或-CN。In certain embodiments, R ³ is F, CI, Br, I or -CN.

在另一態樣中，本發明提供製備如本文所揭示化合物之方法。在各實施例中，該方法可包括分別使式IIa及IIb之化合物In another aspect, the invention provides a method of making a compound as disclosed herein. In various embodiments, the method can include the compounds of Formulas IIa and IIb, respectively.

與硫氰酸鹽反應，其中R¹及R²係如上文所定義，X在每次出現時係H或離去基團，適宜離去基團係F、CI、Br、I、-OSO₂-C₆H₄-CH₃、-OSO₂-CH₃。Reacting with thiocyanate wherein R ¹ and R ² are as defined above, X is H or a leaving group at each occurrence, suitably leaving the group F, CI, Br, I, -OSO ₂ -C ₆ H ₄ -CH ₃ , -OSO ₂ -CH ₃ .

在各實施例中，X在每次出現時可為H或鹵素。舉例而言，X在每次出現時可為H、F、Cl、Br或I。在某些實施例中，X在每次出現時可為H或Br。In various embodiments, X can be H or halogen at each occurrence. For example, X can be H, F, Cl, Br, or I at each occurrence. In certain embodiments, X can be H or Br at each occurrence.

在一些實施例中，硫氰酸鹽係LiSCN、NaSCN、KSCN、NH₄SCN、NR₄SCN、PR₄SCN，其中R各自獨立地係C_1-18烷基、CuSCN或AgSCN。較佳地，硫氰酸鹽係NaSCN或KSCN。In some embodiments, thiocyanate based _{LiSCN, NaSCN, KSCN, NH 4} SCN, NR 4 SCN, PR 4 SCN, wherein each R is independently C _1-18 alkyl-based, or of CuSCN AgSCN. Preferably, the thiocyanate is NaSCN or KSCN.

在一些實施例中，該反應可在室溫(例如，介於約20℃與約30℃之間)下進行。在一些實施例中，該反應可在不同於室溫之溫度下進行。舉例而言，該溫度可低於或高於室溫。在某些實施例中，該反應可在高溫(即，高於室溫之溫度)下進行。舉例而言，高溫可介於50℃與300℃之間。在具體實施例中，高溫可介於50℃與180℃之間，例如，介於70℃與150℃之間(例如，70℃或150℃)。In some embodiments, the reaction can be carried out at room temperature (eg, between about 20 ° C and about 30 ° C). In some embodiments, the reaction can be carried out at a temperature other than room temperature. For example, the temperature can be lower or higher than room temperature. In certain embodiments, the reaction can be carried out at elevated temperatures (i.e., temperatures above room temperature). For example, the high temperature can be between 50 ° C and 300 ° C. In particular embodiments, the elevated temperature may be between 50 °C and 180 °C, for example between 70 °C and 150 °C (eg, 70 °C or 150 °C).

形成氰硫基化合物抑或異氰硫基化合物可視溶劑之性質而定。The formation of a thiocyanato compound or an isocyanato compound may depend on the nature of the solvent.

於其中主要或幾乎只形成氰硫基化合物之溶劑包括DMSO、DMSO與芳香族溶劑(例如甲苯、二甲苯、三甲苯、四氫化萘、氯苯、二氯苯、氯萘或硝基苯)之混合物、或DMSO與醚(例如1,4-二噁烷或四氫呋喃)之混合物。The solvent in which the cyanthio compound is mainly or almost formed includes DMSO, DMSO and an aromatic solvent (for example, toluene, xylene, trimethylbenzene, tetrahydronaphthalene, chlorobenzene, dichlorobenzene, chloronaphthalene or nitrobenzene). Mixture, or a mixture of DMSO and an ether such as 1,4-dioxane or tetrahydrofuran.

於其中主要或幾乎只形成異氰硫基化合物之溶劑包括甲基乙基酮及異丁基甲基酮。在相轉移觸媒(例如四級銨鹽)存在下反應有助於異氰硫基化合物之形成。The solvent in which the isocyanato compound is mainly or almost formed includes methyl ethyl ketone and isobutyl methyl ketone. The reaction in the presence of a phase transfer catalyst (e.g., a quaternary ammonium salt) aids in the formation of the isocyanato compound.

在任一情形下，當形成氰硫基-、異氰硫基-及混合氰硫基-異氰硫基-化合物之混合物時，可藉由標準方法(例如層析)來分離出純淨化合物。In either case, when a mixture of thiocyanato-, isocyanato- and mixed cyanothio-isocyanathio-compounds is formed, the pure compound can be isolated by standard methods such as chromatography.

在各實施例中，式IIa及IIb之化合物分別可藉由分別使式IIIa及IIIb之化合物In various embodiments, the compounds of Formulas IIa and IIb, respectively, can be obtained by separately rendering compounds of Formulas IIIa and IIIb

與一級胺R¹-NH₂或R²-NH₂在非質子溶劑中反應來製備，其中X、R¹及R²係如本文所定義。此較佳用於化合物IIb之製備。Prepared by reaction with a primary amine R ¹ -NH ₂ or R ² -NH ₂ in an aprotic solvent, wherein X, R ¹ and R ² are as defined herein. This is preferably used in the preparation of compound IIb.

然而，在製備化合物IIa之情形下，更佳分別使用氯化試劑及溴化試劑來氯化或溴化式Va之萘二醯亞胺化合物。However, in the case of the preparation of the compound IIa, it is more preferred to chlorinate or bromine the naphthalene diimine compound of the formula Va using a chlorinating reagent and a brominating reagent, respectively.

與溴化萘四甲酸二酐IVa且隨後用R¹-NH₂及/或R²-NH₂醯亞胺化化合物IIIa相比，此可形成較高產率化合物IIa。This results in a higher yield of compound IIa compared to brominated naphthalenetetracarboxylic dianhydride IVa and subsequent imidization of compound IIIa with R ¹ -NH ₂ and/or R ² -NH ₂ oxime.

本發明亦關於製造經溴取代之式IIa之萘二醯亞胺化合物之製程The invention also relates to a process for producing a naphthylquinone imine compound of the formula IIa substituted by bromine

其中X獨立地係H、Cl或Br，條件係至少一個X係Cl或Br，R¹、R²係如請求項1中所定義，該製程包含分別使用氯化試劑及溴化試劑氯化或溴化式Va之萘二醯亞胺之步驟Wherein X is independently H, Cl or Br, and the condition is at least one X-based Cl or Br, and R ¹ and R ² are as defined in claim 1, the process comprising chlorinating with a chlorinating reagent and a brominating reagent, respectively. Step of bromination of naphthalene diimine of formula Va

較佳氯化試劑及溴化試劑分別係N,N'-二氯異氰尿酸及N,N'-二溴異氰尿酸。Preferred chlorinating reagents and brominating reagents are N,N'-dichloroisocyanuric acid and N,N'-dibromoisocyanuric acid, respectively.

氯化較佳係以濃縮硫酸作為反應介質(例如95-98 wt.-%硫酸)實施。可分別添加FeCl₃及FeBr₃作為觸媒。Chlorination is preferably carried out using concentrated sulfuric acid as the reaction medium (e.g., 95-98 wt.-% sulfuric acid). FeCl ₃ and FeBr ₃ may be separately added as a catalyst.

式IIa之萘二醯亞胺化合物較佳藉由使萘四甲酸二酐與一級胺R¹-NH₂、R²-NH₂或其混合物反應來獲得，其中R¹、R²係如本文所定義。The naphthalene diimine compound of the formula IIa is preferably obtained by reacting naphthalenetetracarboxylic dianhydride with a primary amine R ¹ -NH ₂ , R ² -NH ₂ or a mixture thereof, wherein R ¹ and R ² are as herein definition.

在各實施例中，非質子溶劑可包括醚。在一些實施例中，非質子溶劑可包括(C_1-6烷基)O(CH₂CH₂O)_m(C_1-6烷基)，其中m可為1、2、3、4、5或6。在具體實施例中，非質子溶劑可為一種溶劑或包括三乙二醇二甲基醚之溶劑混合物。舉例而言，非質子溶劑可為三乙二醇二甲基醚。In various embodiments, the aprotic solvent can include an ether. In some embodiments, the aprotic solvent can include (C _1-6 alkyl)O(CH ₂ CH ₂ O) _m (C _1-6 alkyl), wherein m can be 1, 2, 3, 4, 5 Or 6. In a particular embodiment, the aprotic solvent can be a solvent or a solvent mixture comprising triethylene glycol dimethyl ether. For example, the aprotic solvent can be triethylene glycol dimethyl ether.

在各實施例中，該反應可在室溫下進行。在各實施例中，該反應可在不同於室溫之溫度下進行。舉例而言，該溫度可低於或高於室溫。在某些實施例中，該反應可在高溫(即，高於室溫之溫度)下進行。舉例而言，高溫可介於50℃與300℃之間。在具體實施例中，高溫可介於50℃與200℃之間，舉例而言，介於70℃與180℃之間(例如，165℃)。In various embodiments, the reaction can be carried out at room temperature. In various embodiments, the reaction can be carried out at a temperature other than room temperature. For example, the temperature can be lower or higher than room temperature. In certain embodiments, the reaction can be carried out at elevated temperatures (i.e., temperatures above room temperature). For example, the high temperature can be between 50 ° C and 300 ° C. In particular embodiments, the elevated temperature may be between 50 °C and 200 °C, for example between 70 °C and 180 °C (eg, 165 °C).

式IIIa及IIIb之化合物分別可藉由使用已知溴化試劑(例如溴、N,N'-二溴異氰尿酸或N-溴琥珀醯亞胺)分別溴化式IVa及IVb之化合物來製備，The compounds of the formulae IIIa and IIIb, respectively, can be prepared by brominating the compounds of the formulae IVa and IVb, respectively, using known brominating reagents such as bromine, N,N'-dibromoisocyanuric acid or N-bromosuccinimide. ,

化合物IVb之溴化闡述於DE 195 47 209及F. Wurthner,Chem. Commun. 2004,1564-1579中。苝二醯亞胺之溴化闡述於J. Org. Chem. 2007,72,5973-5979中。The bromination of compound IVb is described in DE 195 47 209 and F. Wurthner, Chem. Commun. 2004, 1564-1579. The bromination of indole diimine is described in J. Org. Chem. 2007, 72, 5973-5979.

本發明之化合物可按照在下文反應圖1中所概述之程序來製備，此藉由自市售起始材料、參考文獻中已知之化合物或可容易地製備之中間體開始藉由採用熟習此項技術者已知之標準合成方法及程序來達成。用於製備有機分子之標準合成方法及程序以及官能團轉化及操控可自相關科技文獻或自業內標準教科書容易地獲得。應瞭解，除非另有說明，否則當給出典型或較佳製程條件(即，反應溫度、時間、反應物之莫耳比、溶劑、壓力等)時，亦可使用其他製程條件。最佳反應條件可隨所用具體反應物或溶劑而變，但該等條件可由熟習此項技術者藉由常規最優化程序來確定。熟習有機合成技術者應認識到，合成步驟之性質及順序可出於最優化本文所述化合物形成之目的而有所變化。The compounds of the present invention can be prepared according to the procedures outlined in Reaction Scheme 1 below, starting from the use of commercially available starting materials, compounds known in the references, or intermediates which can be readily prepared. Standard synthesis methods and procedures known to the skilled person are used to achieve this. Standard synthetic methods and procedures for the preparation of organic molecules, as well as functional group transformation and manipulation, are readily available from related scientific literature or from industry standard textbooks. It should be understood that other process conditions may also be employed when typical or preferred process conditions (i.e., reaction temperatures, times, molar ratios of reactants, solvents, pressures, etc.) are given unless otherwise indicated. Optimum reaction conditions may vary with the particular reactants or solvents employed, but such conditions can be determined by those skilled in the art by routine optimization procedures. Those skilled in the art of organic synthesis will recognize that the nature and sequence of the synthetic steps may vary for the purpose of optimizing the formation of the compounds described herein.

本文所述方法可按照業內已知之任一適宜方法來監測。舉例而言，產物形成可藉由光譜手段(例如，核磁共振譜(NMR，例如，¹H或¹³C)、紅外光譜(IR)、分光光度計(例如，UV可見光)、質譜(MS))或藉由層析法(例如，高壓液相層析(HPLC)、氣相層析(GC)、凝膠滲透層析(GPC)或薄層層析(TLC))來監測。The methods described herein can be monitored according to any suitable method known in the art. For example, product formation can be by spectroscopic means (eg, nuclear magnetic resonance spectroscopy (NMR, eg, ¹ H or ¹³ C), infrared spectroscopy (IR), spectrophotometer (eg, UV visible light), mass spectrometry (MS)) Or by chromatography (for example, high pressure liquid chromatography (HPLC), gas chromatography (GC), gel permeation chromatography (GPC) or thin layer chromatography (TLC).

本文所述反應或製程可在可由熟習有機合成技術之人員容易地選擇的適宜溶劑中實施。適宜溶劑通常為與反應物、中間體及/或產物在實施反應之溫度(即，可介於溶劑之凝固溫度至該溶劑之沸點溫度之間的溫度)下實質上不反應者。給定反應可在一種溶劑一種以上溶劑之混合物中實施。視具體反應步驟而定，可選擇用於具體反應步驟之適宜溶劑。The reactions or processes described herein can be carried out in a suitable solvent which can be readily selected by those skilled in the art of organic synthesis. Suitable solvents are generally substantially nonreactive with the reactants, intermediates and/or products at the temperature at which the reaction is carried out (i.e., the temperature between the solidification temperature of the solvent and the boiling temperature of the solvent). A given reaction can be carried out in a mixture of one or more solvents in one solvent. Depending on the particular reaction step, suitable solvents for the particular reaction step can be selected.

反應圖1Reaction diagram 1

如在反應圖1中所示，苝-3,4:9,10-四甲酸二酐(PDA) a可在1,7-位經溴化以提供PDA-Br₂ b，b在與一級胺反應後能夠提供雙(二甲醯亞胺) c。c中之溴基經氰硫基取代可產生經二氰硫基取代之雙(二甲醯亞胺) d。儘管未在反應圖1中顯示，但a之溴化亦可產生b之區域異構體，例如，1,6-二溴-苝-3,4:9,10-四甲酸二酐，隨後產生d之區域異構體，例如，1,6-二氰硫基雙(二甲醯亞胺)。代替PDA，由胺化得到之雙(二甲醯亞胺)可以類似方式經溴化，得到化合物c。As shown in the reaction scheme 1, 苝-3,4:9,10-tetracarboxylic dianhydride (PDA) a can be brominated at the 1,7-position to provide PDA-Br ₂ b, b in the primary amine After the reaction, bis(dimethylimine) c can be provided. Substitution of a bromo group in c with a thiocyano group results in a bis(dimethylimineimine) d substituted with a dicyanthio group. Although not shown in the reaction scheme 1, the bromination of a can also produce regioisomers of b, for example, 1,6-dibromo-indole-3,4:9,10-tetracarboxylic dianhydride, which is subsequently produced. A regioisomer of d, for example, 1,6-dicyanothiobis(dimethylimine). Instead of PDA, the bis(dimethylimine imine) obtained by amination can be brominated in a similar manner to give compound c.

以類似方式，萘二氰硫基雙(二甲醯亞胺)可根據反應圖2自萘-3,4:7,8-四甲酸二酐來製備：In a similar manner, naphthalocyanuryl bis(dimethylimine) can be prepared from naphthalene-3,4:7,8-tetracarboxylic dianhydride according to reaction scheme 2:

反應圖2Reaction diagram 2

然而，較佳根據反應圖3製備萘二氰硫基雙(二甲醯亞胺)化合物：However, it is preferred to prepare a naphthalene thiocyanate bis(dimethyl quinone imine) compound according to Reaction Scheme 3:

反應圖3Reaction Figure 3

式I化合物可用於製備半導體材料(例如，組合物及複合物)，該等半導體材料進而可用於製作各種製造物件、結構及裝置。納入一或多種本發明化合物之半導體材料可能呈現n-型半導電活性。The compounds of formula I are useful in the preparation of semiconductor materials (e.g., compositions and composites) which, in turn, can be used in the fabrication of various articles of manufacture, structures, and devices. Semiconductor materials incorporating one or more compounds of the invention may exhibit n-type semiconducting activity.

本文所揭示化合物可溶於常見溶劑中，本發明在製作諸如下列等電裝置中可提供處理優勢：薄膜半導體、場效應裝置、有機發光二極體(OLED)、有機光伏打、光檢測器、電容器及感測器。本文所用當至少1 mg化合物可溶解於1 mL溶劑中時，該化合物可視為可溶於該溶劑中。常見有機溶劑之實例包括石油醚；乙腈；芳香族烴，例如苯、甲苯、二甲苯及三甲苯；酮，例如丙酮及甲基乙基酮；醚，例如四氫呋喃、二噁烷、雙(2-甲氧基乙基)醚、二***、二異丙醚及第三丁基甲基醚；醇，例如甲醇、乙醇、丁醇及異丙醇；脂肪族烴，例如己烷；乙酸酯類，例如乙酸甲酯、乙酸乙酯、甲酸甲酯、甲酸乙酯、乙酸異丙酯及乙酸丁酯；醯胺，例如二甲基甲醯胺及二甲基乙醯胺；亞碸，例如二甲亞碸；鹵化脂肪族及芳香族烴，例如二氯甲烷、氯仿、二氯烯烷、氯苯、二氯苯及三氯苯；及環狀溶劑類，例如環戊酮、環己酮及2-甲基吡咯啶酮。常見無機溶劑之實例包括水及離子液體。The compounds disclosed herein are soluble in common solvents, and the present invention provides processing advantages in the fabrication of isoelectric devices such as thin film semiconductors, field effect devices, organic light emitting diodes (OLEDs), organic photovoltaic devices, photodetectors, Capacitors and sensors. As used herein, when at least 1 mg of the compound is soluble in 1 mL of the solvent, the compound can be considered to be soluble in the solvent. Examples of common organic solvents include petroleum ether; acetonitrile; aromatic hydrocarbons such as benzene, toluene, xylene, and trimethylbenzene; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane, and di(2- Methoxyethyl)ether, diethyl ether, diisopropyl ether and tert-butyl methyl ether; alcohols such as methanol, ethanol, butanol and isopropanol; aliphatic hydrocarbons such as hexane; acetates such as acetic acid Methyl ester, ethyl acetate, methyl formate, ethyl formate, isopropyl acetate and butyl acetate; guanamine, such as dimethylformamide and dimethylacetamide; hydrazine, such as dimethyl hydrazine Halogenated aliphatic and aromatic hydrocarbons such as dichloromethane, chloroform, dichloroolefin, chlorobenzene, dichlorobenzene and trichlorobenzene; and cyclic solvents such as cyclopentanone, cyclohexanone and 2-methyl Pyrrolidone. Examples of common inorganic solvents include water and ionic liquids.

因此，本發明進一步提供包括一或多種溶於或分散於液體介質(例如，有機溶劑、無機溶劑或其組合(例如，有機溶劑之混合物、無機溶劑之混合物、或有機與無機溶劑之混合物))中之本文所揭示化合物的組合物。在一些實施例中，該組合物可進一步包括一或多種獨立地選自下列之添加劑：清潔劑、分散劑、黏合劑、增溶劑、固化劑、起始劑、保濕劑、消泡劑、潤濕劑、pH調節劑、殺生物劑及抑菌劑。舉例而言，表面活性劑及/或其他聚合物(例如，聚苯乙烯、聚乙烯、聚-α-甲基苯乙烯、聚異丁烯、聚丙烯、聚甲基丙烯酸甲酯及諸如此類)可作為分散劑、黏合劑、增溶劑及/或消泡劑納入。在一些實施例中，該等組合物可包括一或多種本文所揭示化合物，舉例而言，可將兩種或更多種不同的本發明化合物溶於有機溶劑中以製備沈積用組合物。在某些實施例中，該組合物可包括兩種或更多種立體異構體。此外，應瞭解，本文所述裝置亦可包含一或多種本發明化合物，例如，兩種或更多種如本文所述立體異構體。Accordingly, the present invention further provides that one or more are dissolved or dispersed in a liquid medium (for example, an organic solvent, an inorganic solvent, or a combination thereof (for example, a mixture of organic solvents, a mixture of inorganic solvents, or a mixture of organic and inorganic solvents)) A composition of a compound disclosed herein. In some embodiments, the composition may further comprise one or more additives independently selected from the group consisting of detergents, dispersants, binders, solubilizers, curing agents, starters, humectants, defoamers, and moisturizers. Wet agent, pH adjuster, biocide and bacteriostatic agent. For example, surfactants and/or other polymers (eg, polystyrene, polyethylene, poly-α-methylstyrene, polyisobutylene, polypropylene, polymethyl methacrylate, and the like) can be dispersed Ingredients, binders, solubilizers and/or defoamers are included. In some embodiments, the compositions can include one or more compounds disclosed herein, for example, two or more different compounds of the invention can be dissolved in an organic solvent to prepare a composition for deposition. In certain embodiments, the composition can include two or more stereoisomers. Furthermore, it is to be understood that the devices described herein can also comprise one or more compounds of the invention, for example, two or more stereoisomers as described herein.

包括各種溶液處理技術在內之各種沈積技術已用於製備有機電子裝置。舉例而言，大部分印刷電子裝置技術已集中在噴墨印刷，主要由於此項技術可更佳地控制特徵位置及多層對齊。噴墨印刷係非接觸製程，其提供如下優點：不需要預成型母片(與接觸印刷技術相比)以及對墨噴出進行數位控制從而提供按需噴墨(drop-on-demand)印刷。微分散係另一種非接觸印刷方法。然而，接觸印刷技術具有十分適於極快輥-對-輥處理之關鍵優勢。實例性接觸印刷技術包括但不限於絲網印刷、凹版印刷、平版印刷、柔版印刷、微影印刷、移印及微接觸印刷。本文所用「印刷」包括非接觸製程，例如，噴墨印刷、微噴印刷(microdispensing)及諸如此類；及接觸製程，例如，絲網印刷、凹版印刷、平版印刷、柔版印刷、微影印刷、移印、微接觸印刷及諸如此類。其他溶液處理技術包括(例如)旋塗、滴注、區域澆注、浸塗、刮塗或噴塗。另外，沈積步驟可藉由真空汽相沈積來實施。Various deposition techniques, including various solution processing techniques, have been used to prepare organic electronic devices. For example, most printed electronic device technologies have focused on inkjet printing, primarily due to the superior control of feature location and multilayer alignment. Inkjet printing is a non-contact process that provides the advantage of not requiring a preformed master (as compared to contact printing techniques) and digitally controlling ink ejection to provide drop-on-demand printing. Microdispersion is another non-contact printing method. However, contact printing technology has a key advantage that is well suited for very fast roll-to-roll processing. Exemplary contact printing techniques include, but are not limited to, screen printing, gravure printing, lithography, flexographic printing, lithography, pad printing, and microcontact printing. As used herein, "printing" includes non-contact processes such as ink jet printing, microdispensing, and the like; and contact processes such as screen printing, gravure printing, lithography, flexography, lithography, and shifting. Printing, microcontact printing and the like. Other solution processing techniques include, for example, spin coating, drip, zone casting, dip coating, knife coating or spray coating. Alternatively, the deposition step can be carried out by vacuum vapor deposition.

因此，本發明進一步提供製備半導體材料之方法。該等方法可包括製備包括一或多種溶於或分散於諸如溶劑或溶劑混合物等液體介質中之本文所揭示化合物的組合物，及在基板上沈積該組合物以提供包括一或多種本文所揭示化合物之半導體材料(例如，薄膜半導體)。在各實施例中，該液體介質可為有機溶劑、諸如水等無機溶劑或其組合。在一些實施例中，該組合物可進一步包括一或多種獨立地選自下列之添加劑：黏度調變劑、清潔劑、分散劑、黏合劑、增溶劑、固化劑、起始劑、保濕劑、消泡劑、潤濕劑、pH調節劑、殺生物劑及抑菌劑。舉例而言，表面活性劑及/或聚合物(例如，聚苯乙烯、聚乙烯、聚-α-甲基苯乙烯、聚異丁烯、聚丙烯、聚甲基丙烯酸甲酯及諸如此類)可作為分散劑、黏合劑、增溶劑及/或消泡劑納入。在一些實施例中，該沈積步驟可藉由印刷來實施，包括噴墨印刷及各種接觸印刷技術(例如，絲網印刷、凹版印刷、平版印刷、移印、微影印刷、柔版印刷及微接觸印刷)。在其他實施例中，沈積步驟可藉由旋塗、滴注、區域澆注、浸塗、刮塗或噴塗來實施。Accordingly, the present invention further provides methods of making semiconductor materials. The methods can include preparing a composition comprising one or more compounds disclosed herein dissolved or dispersed in a liquid medium such as a solvent or solvent mixture, and depositing the composition on a substrate to provide one or more of the disclosed herein. A semiconductor material of a compound (eg, a thin film semiconductor). In various embodiments, the liquid medium can be an organic solvent, an inorganic solvent such as water, or a combination thereof. In some embodiments, the composition may further comprise one or more additives independently selected from the group consisting of viscosity modifiers, detergents, dispersants, binders, solubilizers, curing agents, starters, humectants, Defoamer, wetting agent, pH adjuster, biocide and bacteriostatic agent. For example, surfactants and/or polymers (eg, polystyrene, polyethylene, poly-α-methylstyrene, polyisobutylene, polypropylene, polymethyl methacrylate, and the like) can be used as a dispersing agent. , binders, solubilizers and / or defoamers are included. In some embodiments, the deposition step can be performed by printing, including inkjet printing and various contact printing techniques (eg, screen printing, gravure, lithography, pad printing, lithography, flexography, and micro). Contact printing). In other embodiments, the depositing step can be carried out by spin coating, dripping, zone casting, dip coating, knife coating or spray coating.

包括電子裝置、光學裝置及光電子裝置(例如，場效應電晶體(例如，薄膜電晶體)、光伏打、有機發光二極體(OLED)、互補金屬氧化物半導體(CMOS)、互補倒相器、D型正反器、整流器及環形振盪器)在內之各種可利用本文所揭示化合物及半導體材料之製造物件以及製備其之方法均屬於本發明之範疇。Including electronic devices, optical devices, and optoelectronic devices (eg, field effect transistors (eg, thin film transistors), photovoltaic devices, organic light emitting diodes (OLEDs), complementary metal oxide semiconductors (CMOS), complementary inverters, Various articles, such as D-type flip-flops, rectifiers, and ring oscillators, which can utilize the compounds and semiconductor materials disclosed herein, and methods of making the same are within the scope of the present invention.

因此，本發明提供製造物件，例如本文所述包括具有本發明半導體材料、基板組份及/或電介質組份之複合物之各種裝置。基板組份可選自包括下列之材料：經摻雜矽、氧化銦錫(ITO)、經ITO塗佈之玻璃、經ITO塗佈之聚醯亞胺或其他塑膠、單獨或上面塗佈有聚合物或其他基材之鋁或其他金屬、經摻雜聚噻吩或其他聚合物及諸如此類。電介質組份可自下列物質來製備：諸如各種氧化物(例如，SiO₂、Al₂O₃、HfO₂)等無機電介質材料、諸如各種聚合物材料(例如，聚碳酸酯、聚酯、聚苯乙烯、聚鹵乙烯、聚丙烯酸酯)等有機電介質材料、自組裝超晶格/自組裝奈米電介質(SAS/SAND)材料(例如，闡述於Yoon,M-H.等人，PNAS,102(13): 4678-4682(2005)中)，該文獻之全部揭示內容以引用方式併入本文中)、以及雜合有機/無機電介質材料(例如，闡述於美國專利申請案第11/642,504號中，該專利之全部揭示內容以引用方式併入本文中)。在一些實施例中，電介質組份可包括闡述於美國專利申請案第11/315,076號、第60/816,952號及第60/861,308號中之交聯聚合物摻合物，該等案件各自之全部揭示內容均以引用方式併入本文中。該複合物亦可包括一或多個電觸點。適用於源極、汲極及閘極電極之材料包括金屬(例如，Au、Al、Ni、Cu)、透明導電氧化物(例如，ITO、IZO、ZITO、GZO、GIO、GITO)及導電聚合物(例如，聚(3,4-伸乙基二氧基噻吩)聚(苯乙烯磺酸酯)(PEDOT:PSS)、聚苯胺(PANI)、聚吡咯(PPy))。一或多種本文所述複合物可納入各種有機電子、光學及光電子裝置中，例如，有機薄膜電晶體(OTFT)(特定而言，有機場效應電晶體(OFET))以及感測器、電容器、單極電路、互補電路(例如，反相電路)及諸如此類。Accordingly, the present invention provides articles of manufacture, such as those described herein that include a composite having a semiconductor material, substrate component, and/or dielectric component of the present invention. The substrate component may be selected from the group consisting of doped germanium, indium tin oxide (ITO), ITO coated glass, ITO coated polyimide or other plastic, coated with polymerization alone or on top. Aluminum or other metal of the substrate or other substrate, doped polythiophene or other polymer, and the like. The dielectric component can be prepared from inorganic dielectric materials such as various oxides (eg, SiO ₂ , Al ₂ O ₃ , HfO ₂ ), such as various polymeric materials (eg, polycarbonate, polyester, polyphenylene). Organic dielectric materials such as ethylene, polyvinyl halide, and polyacrylate, self-assembled superlattice/self-assembled nano dielectric (SAS/SAND) materials (for example, as described in Yoon, MH. et al., PNAS, 102(13) : 4678-4682 (2005), the entire disclosure of which is hereby incorporated by reference, in its entirety, and the <RTI ID=0.0>> The entire disclosure of the patent is incorporated herein by reference. In some embodiments, the dielectric component can include a crosslinked polymer blend as described in U.S. Patent Application Serial Nos. 11/315,076, the disclosure of which are incorporated herein to The disclosures are hereby incorporated by reference. The composite may also include one or more electrical contacts. Materials suitable for source, drain and gate electrodes include metals (eg, Au, Al, Ni, Cu), transparent conductive oxides (eg, ITO, IZO, ZITO, GZO, GIO, GITO) and conductive polymers (for example, poly(3,4-extended ethyldioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), polyaniline (PANI), polypyrrole (PPy). One or more of the composites described herein can be incorporated into a variety of organic electronic, optical, and optoelectronic devices, such as organic thin film transistors (OTFTs) (specifically, organic field effect transistors (OFETs)), as well as sensors, capacitors, Unipolar circuits, complementary circuits (eg, inverting circuits), and the like.

因此，本發明之一個態樣關於製作可納入本發明半導體材料之有機場效應電晶體的方法。本發明之半導體材料可用於製作各種有機場效應電晶體，包括頂部閘極頂部觸點電容器結構、頂部閘極底部觸點電容器結構、底部閘極頂部觸點電容器結構及底部閘極底部觸點電容器結構。圖1圖解說明四種常見類型OFET結構：頂部觸點底部閘極結構(左上方)、底部觸點底部閘極結構(右上方)、底部觸點頂部閘極結構(左下方)及頂部觸點頂部閘極結構(右下方)。如圖1中所示，OFET可包括電介質層(例如，顯示為8、8'、8"及8''')、半導體層(例如，顯示為6、6'、6"及6''')、閘極觸點(例如，顯示為10、10'、10"及10''')、基板(例如，顯示為12、12'、12"及12''')以及源極及汲極觸點(例如，顯示為2、2'、2"、2'''、4、4'、4"及4''')。Accordingly, one aspect of the present invention is directed to a method of making an organic field effect transistor that can be incorporated into a semiconductor material of the present invention. The semiconductor material of the present invention can be used to fabricate a variety of organic field effect transistors, including a top gate top contact capacitor structure, a top gate bottom contact capacitor structure, a bottom gate top contact capacitor structure, and a bottom gate bottom contact capacitor. structure. Figure 1 illustrates four common types of OFET structures: top contact bottom gate structure (top left), bottom contact bottom gate structure (top right), bottom contact top gate structure (bottom left), and top contact Top gate structure (bottom right). As shown in FIG. 1, an OFET can include a dielectric layer (eg, shown as 8, 8', 8", and 8"'), a semiconductor layer (eg, shown as 6, 6', 6", and 6''' ), gate contacts (for example, shown as 10, 10', 10", and 10"'), substrates (eg, shown as 12, 12', 12", and 12"'), and source and drain Contacts (eg, shown as 2, 2', 2", 2''', 4, 4', 4", and 4''').

在某些實施例中，可用本發明化合物在經摻雜之矽基板上製作OTFT裝置，在頂部觸點幾何結構中使用SiO₂作為電介質。在具體實施例中，可藉由真空汽相沈積在室溫下或在高溫下沈積納入至少一種本發明化合物之主動半導電層。在其他實施例中，可藉由基於溶液之製程(例如，旋塗或噴墨印刷)來施加納入至少一種本發明化合物之主動半導電層。對於頂部觸點裝置而言，可在該等膜上使用陰影遮罩對金屬觸點實施圖案化。In certain embodiments, the compounds of the present invention can be used in the production of silicon-based OTFT device board of doped SiO _{2 is} used as a dielectric in the top contact geometry. In a particular embodiment, the active semiconducting layer incorporating at least one compound of the invention can be deposited by vacuum vapor deposition at room temperature or at elevated temperatures. In other embodiments, the active semiconducting layer incorporating at least one compound of the invention can be applied by a solution based process (eg, spin coating or ink jet printing). For top contact devices, the metal contacts can be patterned using a shadow mask on the films.

在某些實施例中，可用本發明化合物在塑膠箔上製作OTFT裝置，在頂部閘極底部觸點幾何結構中使用聚合物作為電介質。在具體實施例中，可在室溫下或在高溫下沈積納入至少一種本發明化合物之主動半導電層。在其他實施例中，可藉由如本文所述之旋塗或印刷來施加納入至少一種本發明化合物之主動半導電層。閘極及源極/汲極觸點可由Au、其他金屬或導電聚合物製成且藉由汽相沈積及/或印刷來沈積。In certain embodiments, an OTFT device can be fabricated on a plastic foil using the compounds of the invention, using a polymer as the dielectric in the top gate bottom contact geometry. In a particular embodiment, the active semiconducting layer incorporating at least one compound of the invention can be deposited at room temperature or at elevated temperatures. In other embodiments, the active semiconducting layer incorporating at least one compound of the invention can be applied by spin coating or printing as described herein. The gate and source/drain contacts can be made of Au, other metals or conductive polymers and deposited by vapor deposition and/or printing.

可使用本發明化合物之其他製造物件係光伏打或太陽能電池。本發明之化合物可呈現寬廣的光吸收及/或極高正漂移還原電位，從而使其合意於此等應用。因此，本文所述化合物在光伏打設計中可用作n-型半導體，其包括形成p-n接面之毗鄰p-型半導電材料。該等化合物可呈薄膜半導體形式，其可為沈積於基板上之薄膜半導體之複合物。在該等裝置中採用本發明之化合物係屬於熟習此項技術者之知識範圍。Other articles of manufacture in which the compounds of the invention may be used are photovoltaic or solar cells. The compounds of the present invention can exhibit broad light absorption and/or very high positive drift reduction potentials, making them desirable for such applications. Thus, the compounds described herein can be used as n-type semiconductors in photovoltaic design, including adjacent p-type semiconducting materials that form p-n junctions. The compounds may be in the form of a thin film semiconductor which may be a composite of thin film semiconductors deposited on a substrate. The use of the compounds of the invention in such devices is within the knowledge of those skilled in the art.

因此，本發明之另一態樣係關於製作納入一或多種本發明半導體材料之有機發光電晶體、有機發光二極體(OLED)或有機光伏打裝置的方法。Thus, another aspect of the invention is directed to a method of making an organic light-emitting transistor, an organic light-emitting diode (OLED) or an organic photovoltaic device incorporating one or more of the semiconductor materials of the present invention.

提供下列實例以進一步闡明本發明及方便理解本發明且並非意欲以任何方式限制本發明。The following examples are provided to further illustrate the invention and to facilitate the understanding of the invention and are not intended to limit the invention in any way.

除非另有說明，否則所有試劑均自商業來源購得且未經進一步純化即使用。一些試劑係按照已知程序來合成。無水四氫呋喃(THF)係自鈉/二苯甲酮蒸餾得到。除非另有說明，否則在氮氣中實施反應。使用Cary型1 UV-vis光譜儀記錄UV-Vis譜。在Varian Unity Plus 500分光計及400 MHz分光計上記錄NMR譜(¹H,400 MHz及500 MHz；¹³C,125 MHz)。使用Thermo Finnegan型LCQ Advantage質譜儀實施電噴霧質譜。All reagents were purchased from commercial sources and used without further purification unless otherwise stated. Some reagents were synthesized according to known procedures. Anhydrous tetrahydrofuran (THF) is obtained by distillation from sodium/benzophenone. The reaction was carried out in nitrogen unless otherwise stated. The UV-Vis spectra were recorded using a Cary type 1 UV-vis spectrometer. NMR spectra ( ¹ H, 400 MHz and 500 MHz; ¹³ C, 125 MHz) were recorded on a Varian Unity Plus 500 spectrometer and a 400 MHz spectrometer. Electrospray mass spectrometry was performed using a Thermo Finnegan type LCQ Advantage mass spectrometer.

實例1Example 1 實例1aExample 1a 2,6-二溴-N,N'-雙(1H,1H-全氟丁基)-萘[1,8:4,5]-雙(二甲醯亞胺)之製備Preparation of 2,6-dibromo-N,N'-bis(1H,1H-perfluorobutyl)-naphthalene[1,8:4,5]-bis(dimethylimine)

在室溫下向2.00 g(3.17 mmol)N,N'-雙(1H,1H-全氟丁基)-萘[1,8:4,5]-雙(二甲醯亞胺)[闡述於H. E. Katz等人，Materials Re-search Society Symposium Proceedings(2002),665(Electronics,Optical and Opto-electronic Polymers and Oligomers),271-280中]於240 ml 95%至97%強度之硫酸中之溶液中添加1.17 g(3.96 mmol) 97%強度之N,N'-二溴異氰尿酸。利用鋁箔使反應燒瓶避光。在室溫下將溶液攪拌28小時。隨後，將溶液傾倒至1.5 kg冰上並用NaOH中和。用750 ml二氯甲烷將水相萃取兩次。合併之有機萃取物經硫酸鎂乾燥，過濾並濃縮至乾燥。將殘餘物懸浮於正庚烷中並過濾。將所獲得濾餅乾燥，得到2.29 g黃色固體。在80 ml異丁醇中重結晶，得到2.06 g(理論量之83%)黃色固體，在薄層層析中僅顯示一個斑點。¹H-NMR(400 MHz,D₈-THF)：δ=9.00(s,2H),5.08(t,4H) ppm。To 2.00 g (3.17 mmol) of N,N'-bis(1H,1H-perfluorobutyl)-naphthalene [1,8:4,5]-bis(dimethylimine) at room temperature [discussed in HE Katz et al., Materials Re-search Society Symposium Proceedings (2002), 665 (Electronics, Optical and Opto-electronic Polymers and Oligomers), 271-280] in 240 ml of 95% to 97% strength sulfuric acid solution 1.17 g (3.96 mmol) of 97% strength N,N'-dibromoisocyanuric acid was added. The reaction flask was protected from light by means of aluminum foil. The solution was stirred at room temperature for 28 hours. Subsequently, the solution was poured onto 1.5 kg of ice and neutralized with NaOH. The aqueous phase was extracted twice with 750 ml of dichloromethane. The combined organic extracts were dried with MgSO4, filtered and evaporated. The residue was suspended in n-heptane and filtered. The obtained cake was dried to give 2.29 g of a yellow solid. Recrystallization from 80 ml of isobutanol gave 2.06 g (83% of theory) of yellow solid, which showed only one spot in thin layer chromatography. ¹ H-NMR (400 MHz, D ₈ -THF): δ = 9.00 (s, 2H), 5.08 (t, 4H) ppm.

實例1bExample 1b N,N'-雙(1H,1H-全氟丁基)-2,6-二氰硫基-萘[1,8:4,5]-雙(二甲醯亞胺)之製備Preparation of N,N'-bis(1H,1H-perfluorobutyl)-2,6-dicyanthio-naphthalene[1,8:4,5]-bis(dimethylimide)

在95℃下在2小時內向0.50 g(0.63 mmol) N,N'-雙(1H,1H-全氟丁基)-2,6-二溴-萘[1,8:4,5]雙(二甲醯亞胺)於50 ml二甲亞碸中之溶液中添加0.128 g(1.59 mmol)硫氰酸鈉，同時不斷攪拌。在95℃下將溶液再攪拌1小時並冷卻至室溫。然後將150 ml水添加至反應溶液中，由此形成沉澱。過濾沉澱，用水洗滌並乾燥。將粗產物懸浮於200 ml甲基環己烷中，在回流下加熱1小時並趁熱過濾。用石油醚洗滌濾餅並乾燥。藉此得到0.207 g黃褐色固體，藉由在矽膠上層析將其純化。¹H-NMR(400 MHz,CD₂Cl₂)：δ=9.32(s,2H),5.05(t,4H) ppm。0.50 g (0.63 mmol) of N,N'-bis(1H,1H-perfluorobutyl)-2,6-dibromo-naphthalene [1,8:4,5] bis (within 2 hours at 95 ° C) To a solution of 50 ml of dimethyl hydrazine, 0.128 g (1.59 mmol) of sodium thiocyanate was added while stirring constantly. The solution was stirred at 95 ° C for an additional hour and cooled to room temperature. Then, 150 ml of water was added to the reaction solution, thereby forming a precipitate. The precipitate was filtered, washed with water and dried. The crude product was suspended in 200 ml of methyl cyclohexane, heated under reflux for 1 hour and filtered hot. The filter cake was washed with petroleum ether and dried. Thus 0.207 g of a tan solid was obtained which was purified by chromatography on silica gel. ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ): δ = 9.32 (s, 2H), 5.05 (t, 4H) ppm.

實例2Example 2 N,N'-雙(1H,1H-全氟丁基)-2-異氰硫基-6-氰硫基-萘[1,8:4,5]-雙(二甲醯亞胺)之製備N,N'-bis(1H,1H-perfluorobutyl)-2-isocyanatothio-6-cyanothio-naphthalene [1,8:4,5]-bis(dimethylimine) preparation

在95℃下在3小時內向0.50 g(0.64 mmol) 2,6-二溴-N,N'-雙(1H,1H-全氟丁基)-萘[1,8:4,5]雙(二甲醯亞胺)及0.0056 g(0.013 mmol) Aliquat 134(相轉移觸媒)於50 ml異丁基甲基酮中之溶液中添加0.13 g(1.6 mmol)硫氰酸鈉於異丁基甲基酮中之溶液。在95℃下將溶液再攪拌2小時並冷卻至室溫。在添加3 g矽膠後，將溶液濃縮至乾燥。藉由使用二氯甲烷作為洗脫液在矽膠上層析來純化粗產物。藉此得到0.075 g(理論量之15%)黃褐色固體。¹H-NMR(400 MHz,CD₂Cl₂)：δ=9.28(s,1H),8.70(s,1H),5.06(t,2H),5.00(t,2H) ppm。0.50 g (0.64 mmol) of 2,6-dibromo-N,N'-bis(1H,1H-perfluorobutyl)-naphthalene [1,8:4,5] bis (within 3 hours at 95 ° C) Dimethyl imine) and 0.0056 g (0.013 mmol) Aliquat A solution of 0.13 g (1.6 mmol) of sodium thiocyanate in isobutyl methyl ketone was added to a solution of 134 (phase transfer catalyst) in 50 ml of isobutyl methyl ketone. The solution was stirred at 95 ° C for an additional 2 hours and cooled to room temperature. After adding 3 g of tannin, the solution was concentrated to dryness. The crude product was purified by chromatography on silica gel using dichloromethane as eluent. This gave 0.075 g (15% of theory) of a tan solid. ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ): δ = 9.28 (s, 1H), 8.78 (s, 1H), 5.06 (t, 2H), 5.00 (t, 2H) ppm.

實例3Example 3 N,N'-雙(苯乙基)-1,7(6)-二氰硫基苝[3,4:9,10]-雙(二甲醯亞胺)之製備Preparation of N,N'-bis(phenethyl)-1,7(6)-dicyanothionia[3,4:9,10]-bis(dimethylimine)

將0.50 g(0.65 mmol) 2,6-二溴-N,N'-雙(苯乙基)-苝-[3,4:9,10]雙(二甲醯亞胺)(闡述於US 2007/0259475中)於12 ml二甲亞碸及12 ml氯苯中之溶液加熱至95℃。然後在1小時內緩慢添加0.13 g(1.6 mmol)硫氰酸鈉於15 ml二甲亞碸中之溶液。使反應溶液在此溫度下維持5小時。在將反應溶液冷卻至室溫後，藉由蒸發去除氯苯。添加50 ml水，由此形成沉澱。過濾沉澱，用水及甲醇洗滌且隨後乾燥。藉由使用甲苯/乙酸乙酯(20:1)作為洗脫液在矽膠上層析來純化深紅色粗產物兩次。藉此得到0.11 g(理論量之24%)深紅色固體。¹H-NMR(400 MHz,CD₂Cl₂)：δ=9.09(s,2H),8.80(d,2H),8.47(d,2H),7.10-7.42(m,10H),4.45(t,4H),3.08(t,4H) ppm。0.50 g (0.65 mmol) of 2,6-dibromo-N,N'-bis(phenethyl)-indole-[3,4:9,10] bis(dimethylimine) (described in US 2007) A solution of 12 ml of dimethyl hydrazine and 12 ml of chlorobenzene was heated to 95 ° C in /0259475. A solution of 0.13 g (1.6 mmol) of sodium thiocyanate in 15 ml of dimethyl hydrazine was then slowly added over 1 hour. The reaction solution was maintained at this temperature for 5 hours. After the reaction solution was cooled to room temperature, chlorobenzene was removed by evaporation. 50 ml of water was added, thereby forming a precipitate. The precipitate was filtered, washed with water and methanol and then dried. The deep red crude product was purified twice by chromatography on silica gel using toluene/ethyl acetate (20:1) as eluent. This gave 0.11 g (24% of theory) of a dark red solid. ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ): δ=9.09 (s, 2H), 8.80 (d, 2H), 8.47 (d, 2H), 7.10-7.42 (m, 10H), 4.45 (t, 4H), 3.08 (t, 4H) ppm.

實例4Example 4 實例4aExample 4a N,N'-雙(1-甲基戊基)-1,7(6)-二溴-苝[3,4:9,10]-雙(二甲醯亞胺)之製備Preparation of N,N'-bis(1-methylpentyl)-1,7(6)-dibromo-indole[3,4:9,10]-bis(dimethylimine)

在Roth反應器中將8.03 g(14.6 mmol) 1,7(6)-二溴-苝[3,4:9,10]四甲酸二酐(1,7-與1,6-二溴異構體之混合物)[闡述於DE 19547209中]及3.12 g(30.8 mmol)(S)-(+)-2-胺基己烷於120 ml無水1,4-二噁烷中之懸浮液加熱至160℃並在該溫度下維持1小時，同時不斷攪拌。在將反應溶液冷卻至室溫後，添加450 ml甲醇。將混合物攪拌5小時。過濾沉澱，用甲醇洗滌且隨後乾燥。藉由使用二氯甲烷作為洗脫液在矽膠上層析來純化深紅色粗產物。藉此得到5.24 g(理論量之50%)深紅色固體。¹H-NMR(400 MHz,CDCl₃)：δ=9.48(d,2H),8.90(s,2H),8.69(d,2H),5.28(m,2H),2.24(m,2H),1.92(m,2H),1.60(m,6H),1.35(m,6H),1.25(m,2H),0.87(t,6H) ppm。8.03 g (14.6 mmol) of 1,7(6)-dibromo-indole [3,4:9,10]tetracarboxylic dianhydride (1,7- and 1,6-dibromo isomerization in a Roth reactor) a mixture of the compounds [detailed in DE 19547209] and a suspension of 3.12 g (30.8 mmol) of (S)-(+)-2-aminohexane in 120 ml of anhydrous 1,4-dioxane to 160 °C and maintained at this temperature for 1 hour while continuously stirring. After the reaction solution was cooled to room temperature, 450 ml of methanol was added. The mixture was stirred for 5 hours. The precipitate was filtered, washed with methanol and then dried. The deep red crude product was purified by chromatography on silica gel using dichloromethane as eluent. This gave 5.24 g (50% of theory) of a dark red solid. ¹ H-NMR (400 MHz, CDCl ₃ ): δ=9.48 (d, 2H), 8.90 (s, 2H), 8.69 (d, 2H), 5.28 (m, 2H), 2.24 (m, 2H), 1.92 (m, 2H), 1.60 (m, 6H), 1.35 (m, 6H), 1.25 (m, 2H), 0.87 (t, 6H) ppm.

實例4bExample 4b N,N'-雙(1-甲基戊基)-1,7(6)-二氰硫基-苝[3,4:9,10]-雙(二甲醯亞胺)之製備Preparation of N,N'-bis(1-methylpentyl)-1,7(6)-dicyanothio-indole[3,4:9,10]-bis(dimethylimine)

在95℃下在1.5小時內向0.50 g(0.70 mmol) N,N'-雙(1-甲基戊基)-1,7(6)-二溴-苝[3,4:9,10]雙(二甲醯亞胺)於25 ml二甲亞碸中之溶液中添加0.12 g(1.5 mmol)硫氰酸鈉於10 ml二甲亞碸中之溶液，同時不斷攪拌。在95℃下將溶液再攪拌21小時並冷卻至室溫。然後將150 ml水添加至溶液中，由此形成沉澱。過濾沉澱，用水及甲醇洗滌且隨後乾燥。藉由使用二氯甲烷作為洗脫液在矽膠上層析來純化深紅色粗產物。藉此得到0.30 g(理論量之64%)深紅色固體。根據¹H NMR譜，1,6-二氰硫基異構體之比例為11%。1,7-二氰硫基異構體之¹H NMR(500 MHz,CDCl₃)：δ=9.10(s,2H),8.80(d,2H),8.47(d,2H),5.29(m,2H),2.23(m,2H),1.94(m,2H),1.61(m,6H),1.35(m,6H),1.25(m,2H),0.88(t,6H) ppm。0.50 g (0.70 mmol) of N,N'-bis(1-methylpentyl)-1,7(6)-dibromo-indole [3,4:9,10] in 1.5 hours at 95 °C (Dimethyl imidate) A solution of 0.12 g (1.5 mmol) of sodium thiocyanate in 10 ml of dimethyl hydrazine was added to a solution of 25 ml of dimethyl hydrazine while stirring constantly. The solution was stirred at 95 ° C for an additional 21 hours and cooled to room temperature. Then 150 ml of water was added to the solution, thereby forming a precipitate. The precipitate was filtered, washed with water and methanol and then dried. The deep red crude product was purified by chromatography on silica gel using dichloromethane as eluent. This gave 0.30 g (64% of theory) of a dark red solid. According to the ¹ H NMR spectrum, the ratio of the 1,6-dicyanothio isomer was 11%. ¹ H NMR (500 MHz, CDCl ₃ ) of 1,7-dicyanothio isomer: δ = 9.10 (s, 2H), 8.80 (d, 2H), 8.47 (d, 2H), 5.29 (m, 2H), 2.23 (m, 2H), 1.94 (m, 2H), 1.61 (m, 6H), 1.35 (m, 6H), 1.25 (m, 2H), 0.88 (t, 6H) ppm.

1,6-二氰硫基異構體之¹H NMR(500 MHz,CDCl₃)：δ=9.12(s,2H),8.81(d,2H),8.40(d,2H) ppm；將僅指派芳香族區域中之信號。 ¹ H NMR (500 MHz, CDCl ₃ ) of 1,6-dicyanothio isomer: δ = 9.12 (s, 2H), 8.81 (d, 2H), 8.40 (d, 2H) ppm; Signal in the aromatic region.

可藉由在異丙醇中重結晶來獲得純1,7-二氰硫基異構體，熔點為229℃至230℃(自225℃起分解)。The pure 1,7-dicyanothio isomer can be obtained by recrystallization from isopropanol at a melting point of 229 ° C to 230 ° C (decomposed from 225 ° C).

實例5Example 5 2,6(7)-二氯-N,N'-雙(1H,1H-全氟丁基)-萘[1,8:4,5]-雙(二甲醯亞胺)與2,6,7-三氯-N,N'-雙(1H,1H-全氟丁基)-萘[1,8:4,5]-雙(二甲醯亞胺)之混合物之製備2,6(7)-Dichloro-N,N'-bis(1H,1H-perfluorobutyl)-naphthalene [1,8:4,5]-bis(dimethylimine) and 2,6 Preparation of a mixture of 7-trichloro-N,N'-bis(1H,1H-perfluorobutyl)-naphthalene [1,8:4,5]-bis(dimethylimine)

向0,50 g(0,79 mmol) N,N'-雙(1H,1H-全氟丁基)-萘[1,8:4,5]-雙(二甲醯亞胺)(闡述於H. E. Katz等人Materials Research Society Symposium Proceedings(2002),665(Electronics,Optical and Optoelectronic Polymers and Oligomers),271-280中)於60 ml 95-97 wt.%硫酸中之溶液中添加1,06 g(5,4 mmol)N,N'-二氯-異氰尿酸。在室溫下攪拌30 min後，將溶液加熱至85℃並在此溫度下維持24 h。將反應溶液冷卻至室溫並用1 l冰水稀釋，由此沉澱出黃色固體。將懸浮液攪拌1 h且然後用稀NaOH中和。藉由玻璃料來分離固體並用溫水洗滌。向乾固體中添加二氯甲烷。過濾黃色溶液並蒸發至乾燥。乾燥殘餘物並藉由使用矽膠及二氯甲烷/環己烷(65:35)作為移動相實施層析來純化。獲得兩個主要流份且各自經蒸發及濃縮得到黃色固體。一個流份為0.18 g(理論量之33%)，根據¹H-NMR數據，其含有50重量%三氯化合物及50重量%兩種異構二氯化合物。另一流份為0.070 g(理論量之13%)，根據¹H-NMR數據，其含有66重量%三氯化合物及34重量%兩種異構二氯化合物。0,50 g (0,79 mmol) N,N'-bis(1H,1H-perfluorobutyl)-naphthalene [1,8:4,5]-bis(dimethylimine) HE Katz et al. Materials Research Society Symposium Proceedings (2002), 665 (Electronics, Optical and Optoelectronic Polymers and Oligomers, 271-280) added 1,06 g to a solution of 60 ml of 95-97 wt.% sulfuric acid ( 5,4 mmol) N,N'-dichloro-isocyanuric acid. After stirring at room temperature for 30 min, the solution was heated to 85 ° C and maintained at this temperature for 24 h. The reaction solution was cooled to room temperature and diluted with 1 l of ice water, whereby a yellow solid precipitated. The suspension was stirred for 1 h and then neutralized with dilute NaOH. The solid was separated by a frit and washed with warm water. Dichloromethane was added to the dry solid. The yellow solution was filtered and evaporated to dryness. The residue was dried and purified by chromatography using methylene chloride and dichloromethane/hexanes (65:35) as mobile phase. Two major fractions were obtained and each was evaporated and concentrated to give a yellow solid. One fraction was 0.18 g (33% of theory), and based on ¹ H-NMR data, it contained 50% by weight of a trichloro compound and 50% by weight of two isomeric dichloro compounds. The other fraction was 0.070 g (13% of theory) based on ¹ H-NMR data, which contained 66% by weight of a trichloro compound and 34% by weight of two isomeric dichloro compounds.

2．．．源極觸點2. . . Source contact

2'．．．源極觸點2'. . . Source contact

2"．．．源極觸點2"...source contact

2'''．．．源極觸點2'''. . . Source contact

4．．．汲極觸點4. . . Bungee contact

4'．．．汲極觸點4'. . . Bungee contact

4"．．．汲極觸點4"...bungee contact

4'''．．．汲極觸點4'''. . . Bungee contact

6．．．半導體層6. . . Semiconductor layer

6'．．．半導體層6'. . . Semiconductor layer

6"．．．半導體層6"...semiconductor layer

6'''．．．半導體層6'''. . . Semiconductor layer

8．．．電介質層8. . . Dielectric layer

8'．．．電介質層8'. . . Dielectric layer

8"．．．電介質層8"...dielectric layer

8'''．．．電介質層8'''. . . Dielectric layer

10．．．閘極觸點10. . . Gate contact

10'．．．閘極觸點10'. . . Gate contact

10"．．．閘極觸點10"...gate contact

10'''．．．閘極觸點10'''. . . Gate contact

12．．．基板12. . . Substrate

12'．．．基板12'. . . Substrate

12"．．．基板12"...substrate

12'''．．．基板12'''. . . Substrate

圖1圖解說明場效應電晶體之不同組態。Figure 1 illustrates the different configurations of field effect transistors.

2．．．源極觸點2. . . Source contact

2'．．．源極觸點2'. . . Source contact

2"．．．源極觸點2"...source contact

2'''．．．源極觸點2'''. . . Source contact

4．．．汲極觸點4. . . Bungee contact

4'．．．汲極觸點4'. . . Bungee contact

4"．．．汲極觸點4"...bungee contact

4'''．．．汲極觸點4'''. . . Bungee contact

6．．．半導體層6. . . Semiconductor layer

6'．．．半導體層6'. . . Semiconductor layer

6"．．．半導體層6"...semiconductor layer

6'''．．．半導體層6'''. . . Semiconductor layer

8．．．電介質層8. . . Dielectric layer

8'．．．電介質層8'. . . Dielectric layer

8"．．．電介質層8"...dielectric layer

8'''．．．電介質層8'''. . . Dielectric layer

10．．．閘極觸點10. . . Gate contact

10'．．．閘極觸點10'. . . Gate contact

10"．．．閘極觸點10"...gate contact

10'''．．．閘極觸點10'''. . . Gate contact

12．．．基板12. . . Substrate

12'．．．基板12'. . . Substrate

12"．．．基板12"...substrate

12'''．．．基板12'''. . . Substrate

Claims (10)

一種式I化合物， 其中：R¹及R²在每次出現時獨立地選自-CF₃、-C₂F₅、-C₃F₇及-CH₂C₃F₇；R³獨立地選自鹵素、-CN、-NO₂、-C(O)O(C_1-14烷基)、-C(O)O(C_6-14芳基)、-CHO、C_1-14烷基碸基、C_6-14芳基碸基、磺酸C_1-14烷基酯基或C_6-14芳基酯基、-CONH₂、-CONH(C_1-14烷基)、-CONH(C_6-14芳基)、-CON(C_1-14烷基)₂、-CON(C_1-14烷基)(C_6-14芳基)、-CON(C_6-14芳基)₂、-C(O)H、C_1-14烷氧基、C_1-14烷硫基、C_6-14芳氧基、C_6-14芳硫基、C_1-14烷基、3至14員雜環烷基、C_6-20芳基及5至20員雜芳基；且n係0；x係0； 若z係0，則y係1、2、3或4，且若z>0，則y係0、1、2、3或4；若y係0，則z係1、2、3或4，且若y>0，則z係0、1、2、3或4。 a compound of formula I, Wherein: R ¹ and R ² are independently selected from -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ and -CH ₂ C ₃ F ₇ at each occurrence; R ^{3 is} independently selected from halogen, -CN , -NO ₂ , -C(O)O(C _1-14 alkyl), -C(O)O(C _6-14 aryl), -CHO, C _1-14 alkyl fluorenyl, C _{6- 14} aryl fluorenyl, sulfonyl C _1-14 alkyl ester or C _6-14 aryl ester group, -CONH ₂ , -CONH(C _1-14 alkyl), -CONH (C _6-14 aryl) ), -CON(C _1-14 alkyl) ₂ , -CON(C _1-14 alkyl)(C _6-14 aryl), -CON(C _6-14 aryl) ₂ , -C(O) H, C _1-14 alkoxy, C _1-14 alkylthio, C _6-14 aryloxy, C _6-14 arylthio, C _1-14 alkyl, 3 to 14 membered heterocycloalkyl, C _6-20 aryl and 5 to 20 membered heteroaryl; and n is 0; x is 0; if z is 0, then y is 1, 2, 3 or 4, and if z > 0, then y is 0 1, 2, 3 or 4; if y is 0, then z is 1, 2, 3 or 4, and if y > 0, then z is 0, 1, 2, 3 or 4. 如請求項1之化合物，其中x=0，y=0且z=2。 The compound of claim 1, wherein x = 0, y = 0, and z = 2. 如請求項1之化合物，其中x=0，y=1且z=1。 The compound of claim 1, wherein x = 0, y = 1 and z = 1. 如請求項1之化合物，其中x=0，y=2且z=0。 The compound of claim 1, wherein x = 0, y = 2, and z = 0. 如請求項1之化合物，該化合物具有式Id、Ie或If： 其中R¹及R²係如請求項1中所定義。 The compound of claim 1, which has the formula Id, Ie or If: Wherein R ¹ and R ² are as defined in claim 1. 一種薄膜半導體，其包含一或多種如請求項1之化合物。 A thin film semiconductor comprising one or more compounds as claimed in claim 1. 一種場效應電晶體裝置，其包含如請求項6之薄膜半導體。 A field effect transistor device comprising the thin film semiconductor of claim 6. 一種光伏打裝置，其包含如請求項6之薄膜半導體。 A photovoltaic device comprising the thin film semiconductor of claim 6. 一種有機發光二極體裝置，其包含如請求項6之薄膜半導體。 An organic light emitting diode device comprising the thin film semiconductor of claim 6. 一種單極或互補電路裝置，其包含如請求項6之薄膜半導體。A unipolar or complementary circuit device comprising the thin film semiconductor of claim 6.