CN108164485B - 化合物及其有机电子装置 - Google Patents

化合物及其有机电子装置 Download PDF

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CN108164485B
CN108164485B CN201711236047.8A CN201711236047A CN108164485B CN 108164485 B CN108164485 B CN 108164485B CN 201711236047 A CN201711236047 A CN 201711236047A CN 108164485 B CN108164485 B CN 108164485B
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carbon atoms
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CN108164485A (zh
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廖良玓
吴蕙玲
谢淑珠
陈济中
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Weihai Xinshixun Optoelectronics Co ltd
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Shanghai Nichem Fine Chemical Co Ltd
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Abstract

本发明提供化合物及其有机电子装置，化合物如下式(I)所示，其中X1和X2各自独立为C(Ra)，该二(Ra)彼此相同或不同，该二(Ra)相互连接形成芳香环；X3和X4各自独立为C(Rb)，该二(Rb)彼此相同或不同，该二(Rb)相互连接形成具有至少一呋喃基、至少一噻吩基或至少一二氧化噻吩基的杂芳环。
Figure DDA0001488987360000011

Description

化合物及其有机电子装置
技术领域
本发明是关于一种新颖化合物以及一种使用其的有机电子装置，尤指一种用于电子传输层的新颖化合物以及使用其的有机电子装置。
背景技术
随着科技的进步，各种使用有机材料制成的有机电子装置蓬勃发展，常见的有机电子装置如有机发光二极管(organic light emitting device，OLED)、有机光敏晶体管(organic phototransistor)、有机光伏打电池(organic photovoltaic cell)和有机光检测器(organic photodetector)。
OLED最初是由伊士曼柯达公司(Eastman Kodak)所发明并提出，伊士曼柯达公司的邓青云博士和Steven VanSlyke以真空蒸镀法(vacuum evaporation method)于形成有有机芳香二元胺电洞传输层的透明氧化铟锡(indium tin oxide，ITO)玻璃上沉积电子传输材料{例如三(8-羟基喹啉)铝[tris(8-hydroxyquinoline)aluminum(III)，简称为Alq3]}；再于电子传输层上沉积金属电极，即可完成OLED的制作。OLED因兼具反应速率快、质轻、薄形化、广视角、亮度高、对比高、无需设置背光源以及低耗能的优点，因此备受关注，但OLED仍具有低效率和寿命短的问题。
为了克服低效率的问题，其中一种改善方式为于阴极和阳极间设置中间层，请参阅图1所示，改良的OLED依序设置有基板11、阳极12、电洞注入层13(hole injectionlayer，HIL)、电洞传输层14(hole transport layer，HTL)、发光层15(an emitting layer，EL)、电子传输层16(electron transport layer，ETL)、电子注入层17(electroninjection layer，EIL)和阴极18。当于阳极12和阴极18施加电压时，由阳极12射出的电洞会穿过HIL和HTL并移动至EL，而由阴极18射出的电子会穿过EIL和ETL移动至EL，使电洞和电子在EL层重组成激子(exciton)，当激子由激发态衰退返回基态时即可产生光线。
另一改善方式为改良OLED中ETL的材料，使电子传输材料展现出电洞阻挡能力，传统的电子传输材料包括3,3′-[5′-[3-(3-吡啶基)苯基][1,1′:3′,1″-三联苯]-3,3″-二基]联吡啶{(3,3′-[5′-[3-(3-pyridinyl)phenyl][1,1′:3′,1″-terphenyl]-3,3″-diyl]bispyridine，TmPyPb}、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯[1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene，TPBi]、三(2,4,6-三甲基-3-(3-吡啶基)苯基)硼烷[tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane，3TPYMB]、1,3-二(3,5-二吡啶-3-基-苯基)苯[1,3-bis(3,5-dipyrid-3-yl-phenyl)benzene，BmPyPb]和9,10-二(3-(3-吡啶基)苯基)蒽[9,10-bis(3-(pyridin-3-yl)phenyl)anthracene，DPyPA]。
然而，即使使用了所述电子传输材料，OLED的电流效率仍具有可改善的空间，因此，本发明提供了一种新颖的化合物以克服传统低电流效率的问题。
发明内容
本发明的目的为提供一种新颖化合物，其可用于有机电子装置。
本发明的另一目的为提供一种使用该新颖化合物的有机电子装置，藉此降低有机电子装置的驱动电压。
再者，本发明的另一目的为提供一种使用该新颖化合物的有机电子装置，藉此提升有机电子装置的效率。
为达上述目的，本发明的新颖化合物如下式(I)所示：
Figure BDA0001488987340000021
其中，X1和X2各自独立为C(Ra)，该二(Ra)彼此相同或不同，该二(Ra)相互连接形成芳香环；
其中，X3和X4各自独立为C(Rb)，该二(Rb)彼此相同或不同，该二(Rb)相互连接形成具有至少一呋喃基(furan group)、至少一噻吩基(thiophene group)或至少一二氧化噻吩基(thiophene S,S-dioxide group)的杂芳环；
其中，Z1至Z12各自独立选自于由下列所构成的群组：氢原子、氘原子、三氟甲基(trifuloromethyl group)、卤基、氰基、硝基、碳数为1至40的烷基、碳数为2至40的烯基、碳数为2至40的炔基、环上碳数为3至60的环烷基、环上碳数为3至60的杂环烷基、环上碳数为6至60的芳香基、环上碳数为3至60的杂芳基、碳数为1至40的烷氧基、环上碳数为6至60的芳氧基、碳数为1至40的硅烷基(alkylsilyl group)、环上碳数为6至60的芳硅基(arylsilylgroup)、碳数为1至40的硼烷基(alkylboron group)、环上碳数为6至60的芳硼基(alkylboron group)、碳数为1至40的膦基(phosphine group)和碳数为1至40的氧膦基(phosphine oxide group)。
根据本发明，式(I)中X1和X2包含的双键和该二(Ra)连接形成的键相互共轭且构成该芳香环；相同的，式(I)中X3和X4包含的双键和该二(Rb)连接形成的键相互共轭且构成该杂芳环。根据本发明，自X1和X2延伸形成的该芳香环和自X3和X4延伸形成的该杂芳环相互连接并合，且该芳香环的双键和该杂芳环的双键相互共轭。
较佳的，Z1至Z12各自独立选自于由下列所构成的群组：氢原子、氘原子、三氟甲基、卤基、氰基、硝基、碳数为1至12的烷基、碳数为2至12的烯基、碳数为2至12的炔基、环上碳数为3至30的环烷基、环上碳数为3至30的杂环烷基、环上碳数为6至30的芳香基、环上碳数为3至30的杂芳基、碳数为1至12的烷氧基、环上碳数为6至30的芳氧基、碳数为1至12的硅烷基、环上碳数为6至30的芳硅基、碳数为1至12的硼烷基、环上碳数为6至30的芳硼基、碳数为1至12的膦基和碳数为1至12的氧膦基。
较佳的，式(I)中由X3和X4延伸形成的该杂芳环具有至少一呋喃基。例如，该杂芳环可以是苯并呋喃环(benzofuran ring)、二苯并呋喃环(dibenzofuran ring)或萘并呋喃环(napththofuran ring)，但不限于此。
当自X3和X4延伸的杂芳环包含有至少一呋喃基时，该化合物可表示如下式(I-I)至(I-VI)：
Figure BDA0001488987340000031
Figure BDA0001488987340000041
较佳的，式(I)中由X3和X4延伸形成的该杂芳环具有至少一噻吩基。例如，该杂芳环可以是苯并噻吩环(benzothiophene ring)、二苯并噻吩环(dibenzothiophene ring)或萘并噻吩环(napththothiophene ring)，但不限于此。
当自X3和X4延伸的杂芳环包含有至少一噻吩基时，该化合物可表示如下式(I-VII)至(I-XII)：
Figure BDA0001488987340000042
Figure BDA0001488987340000051
当自X3和X4延伸的杂芳环包含有至少一二氧化噻吩基时，该化合物可表示如下式(I-XIII)至(I-XVIII)：
Figure BDA0001488987340000052
根据本发明，上述A1和A2各自独立为C(Rc)，该二(Rc)彼此相同或不同，该二(Rc)相互连接形成芳香结构，该芳香结构包含在由前述X3和X4所延伸成型的杂芳环中。
较佳的，该芳香结构为经取代或未经取代且碳数为6至20的芳香环状结构。例如：经取代或未经取代的苯环结构(benzene structure)、经取代或未经取代的萘环结构(naphthalene structure)、经取代或未经取代的蒽环结构(anthracene structure)、经取代或未经取代的菲环结构(phenanthrene structure)、经取代或未经取代的芴环结构(fluorene structure)、经取代或未经取代的芘环结构(pyrene structure)、经取代或未经取代的苯并菲结构(benzophenanthrene structure)、经取代或未经取代的苯并芘结构(benzopyrene structure)、经取代或未经取代的荧蒽环结构(fluoranthene structure)或经取代和未经取代的苯并荧蒽环结构(benzofluoranthene structure)，但不限于此；该碳数为6至20的芳香环状结构上的取代基可以为以下基团，但不限于：卤基、氰基、硝基、碳数为1至12的烷基、碳数为2至12的烯基或碳数为2至12的炔基。
较佳的，上述任一通式中由X1和X2所延伸形成的该芳香环为经取代或未经取代且碳数为6至60的碳环；更佳的，由X1和X2所延伸形成的该芳香环为经取代或未经取代且碳数为6至20的碳环。例如：该经取代或未经取代且碳数为6至60的碳环可选自于由下列所构成的群组：经取代或未经取代的苯环、经取代或未经取代的萘环、经取代或未经取代的蒽环、经取代或未经取代的菲环、经取代或未经取代的芴环、经取代或未经取代的芘环、经取代或未经取代的苯并菲环、经取代或未经取代的苯并芘环、经取代或未经取代的荧蒽环和经取代和未经取代的苯并荧蒽环，但不限于此。更佳的，该经取代或未经取代且碳数为6至60的碳环为经取代或未经取代的苯环结构。该碳数为6至20的碳环上的取代基可以为以下基团：卤基、氰基、硝基、碳数为1至12的烷基、碳数为2至12的烯基或碳数为2至12的炔基，但不限于此。
较佳的，该上述任一通式中的Z1至Z8中至少一者是选自于由下列所构成的群组：具有至少一官能基且碳数为1至40的烷基、具有至少一官能基且碳数为2至40的烯基、具有至少一官能基且碳数为2至40的炔基、具有至少一官能基且环上碳数为3至60的环烷基、具有至少一官能基且环上碳数为3至60的杂环烷基、具有至少一官能基且环上碳数为6至60的芳香基、具有至少一氮原子且环上碳数为3至60的杂芳基、具有至少一官能基且碳数为1至40的烷氧基、具有至少一官能基且环上碳数为6至60的芳氧基、具有至少一官能基且碳数为1至40的硅烷基、具有至少一官能基且环上碳数为6至60的芳硅基、具有至少一官能基且碳数为1至40的硼烷基、具有至少一官能基且环上碳数为6至60的芳硼基、具有至少一官能基且碳数为1至40的膦基和具有至少一官能基且碳数为1至40的氧膦基；而上述任一通式中的Z1至Z8中的其他者可以为氢原子、氘原子或说明书提及的其他取代基。该官能基选自于由氰基、硝基、三氟甲基、氟基和氯基所构成的群组。
具体而言，上述任一通式中的Z1至Z8中至少一者是特定的芳香取代基，且该特定的芳香取代基是选自于由下列所构成的群组：
Figure BDA0001488987340000071
Figure BDA0001488987340000081
其中，R1至R7各自独立选自于由下列所构成的群组：氢原子、氘原子、三氟甲基、卤基、氰基、硝基、碳数为1至12的烷基、碳数为2至12的烯基、碳数为2至12的炔基、环上碳数为3至30的环烷基、环上碳数为3至30的杂环烷基、环上碳数为6至30的芳香基、环上碳数为3至20的杂芳基、碳数为1至40的烷氧基、环上碳数为6至30的芳氧基、碳数为1至40的硅烷基、环上碳数为6至30的芳硅基、碳数为1至40的硼烷基、环上碳数为6至30的芳硼基、碳数为1至30的膦基和碳数为1至30的氧膦基；
其中，n为0至4的正整数；m为0至3的正整数；o是0至3的正整数；m和o的总和小于或等于5。
较佳的，R1至R3各自独立为苯基、吡啶基、嘧啶基、吡嗪基、哒嗪基、苯并吡啶基、苯并嘧啶基、苯并吡嗪基或苯并哒嗪基，但不限于此。
于其中一实施方式中，上述任一通式中的Z1至Z8中至少一者为
Figure BDA0001488987340000082
其中，R1可以是吡啶基或苯氰基(cyanophenyl)，R2和R3可以是上述的任一取代基。
于另一实施方式中，上述任一通式中的Z1至Z8中至少一者为
Figure BDA0001488987340000083
其中，R2可以是吡啶基或苯氰基，R1和R3可以是上述的任一取代基。
于再一实施方式中，上述任一通式中的Z1、Z2、Z3、Z6、Z7和Z8中至少一者是经二苯基、二吡啶基、二嘧啶基、二吡嗪基、二哒嗪基、二苯并吡啶基、二苯并嘧啶基、二苯并吡嗪基或二苯并哒嗪基取代的的三嗪基(triazine group)。
较佳的，上述任一通式中的Z1、Z2、Z3、Z6、Z7和Z8中至少一者是前述特定的芳香取代基，而Z4、Z5各自独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为1至12的烷基、碳数为2至12的烯基和碳数为2至12的炔基。或者，上述任一通式中的Z2、Z3、Z6和Z7中至少一者是前述特定的芳香取代基，而Z1、Z4、Z5、Z8各自独立选自于由下列所构成的群组：氢原子、氘原子、碳数为1至12的烷基、碳数为2至12的烯基和碳数为2至12的炔基。
较佳的，上述任一通式中的Z2、Z3、Z6和Z7中至少一者是选自于由下列所构成的群组：
Figure BDA0001488987340000091
Figure BDA0001488987340000101
更佳的，上述任一通式中的Z9至Z12可各自独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为1至12的烷基、碳数为2至12的烯基和碳数为2至12的炔基。
根据本发明，上述任一通式中的的Z1和Z8可以是相同或是不同，Z2和Z7可以是相同或是不同，Z3和Z6可以是相同或是不同；于其中一实施例，Z1、Z2、Z3、Z6、Z7和Z8中的任其中二者可以是上述相同的取代基，而Z1、Z2、Z3、Z6、Z7和Z8中其他者可以选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为1至12的烷基、碳数为2至12的烯基和碳数为2至12的炔基。
举例而言，上述任一通式中的Z1及Z4至Z8可各自独立为氢原子或氘原子，Z2及/或Z3可以是上述特定的芳香取代基。或者，Z1、Z2、Z4、Z5、Z7和Z8可各自独立为氢原子或氘原子，且Z3及Z6二者皆是上述特定的芳香取代基。
举例而言，化合物可以选自于由下列所构成的群组：
Figure BDA0001488987340000102
Figure BDA0001488987340000111
Figure BDA0001488987340000121
Figure BDA0001488987340000131
Figure BDA0001488987340000141
Figure BDA0001488987340000151
Figure BDA0001488987340000161
Figure BDA0001488987340000171
Figure BDA0001488987340000181
Figure BDA0001488987340000191
Figure BDA0001488987340000201
Figure BDA0001488987340000211
Figure BDA0001488987340000221
本发明提供了一种有机电子装置，该有机电子装置包括第一电极、第二电极和设置于该第一电极和该第二电极间的有机层，该有机层具有前述化合物。
较佳的，该有机电子装置为有机发光二极管。更佳的，本发明的新颖化合物可被用于形成电子传输层或电洞阻挡层的材料。
具体而言，该有机发光二极管包括：电洞注入层、电洞传输层、发光层、电子传输层和电子注入层；该电洞注入层形成于该第一电极上；该电洞传输层形成于该电洞注入层上；该发光层形成于该电洞传输层上；该电子传输层形成于该发光层上；该电子注入层形成于该电子传输层和该第二电极之间。
于其中一实施例，该有机层可以为电子传输层，即该电子传输层包含前述的新颖化合物。
较佳的，该电洞注入层可以为双层结构，即该OLED于第一电极和电洞传输层之间具有第一电洞注入层和第二电洞注入层。
较佳的，该电洞传输层亦可以为双层结构，即该OLED于电洞注入层的双层结构与发光层之间具有第一电洞传输层和第二电洞传输层。
较佳的，该电子传输层是由该新颖化合物(如所述化合物I至CCLXII)所制成，本发明以该新颖化合物作为电子传输层材料的OLED相较于商业上的OLED具有较佳的电流效率。其中，商业上OLED中使用的已知电子传输层材料如2-{4-[9,10-二(2-萘基)-2-蒽基]苯基}-1-苯基-1H-苯并[d]咪唑{2-[4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl]-1-phenyl-1H-benzo[d]imidazole}、二(2-甲基-8-羟基喹啉)(p-苯基苯酚)铝[bis(2-methyl-8-quinolinolato)(p-phenylphenolato)aluminum]或2-(4-联苯基)-5-(4-叔丁苯基)-1,3,4-恶二唑[2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole)，PBD]。
较佳的，该OLED包括电洞阻挡层，该电洞阻挡层形成于电子传输层和发光层之间，可防止电洞由发光层移动至电子传输层，所述电洞阻挡层可由所述化合物、2,9-二甲基-4,7-联苯基-1,10-邻二氮杂菲(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline，BCP)或2,3,5,6-四甲基-1-苯基-1,4-邻苯二甲酰亚胺[2,3,5,6-tetramethyl-phenyl-1,4-(bis-phthalimide)，TMPP]所形成，但不限于上述。于另一实施例，该有机层可以为电洞阻挡层，该电洞阻挡层具有前述新颖化合物。
较佳的，该OLED包括电子阻挡层，该电子阻挡层形成于电洞传输层和发光层之间，可防止电子由发光层移动至电洞传输层，所述电子阻挡层可由9,9’-(1,1’-联苯基)-4,4’-二基二-9H-咔唑[9,9'-(1,1'-biphenyl)-4,4'-diylbis-9H-carbazole，CBP]或4,4',4”-三(N-咔唑基)三苯胺[4,4',4”-tri(N-carbazolyl)-triphenylamine，TCTA]所形成，但不限于上述。
当OLED设置有电洞阻挡层和/或电子阻挡层于时，本发明的OLED相较于传统的OLED具有较高的发光效率。
所述第一和第二电洞传输层可由N,N'-(联苯-4,4’-二基)二(N1-(1-萘基))-N4,N4'-二苯基苯-1,4-二胺[N1,N1’-(biphenyl-4,4'-diyl)bis(N1-(naphthalen-1-yl)-N4,N4’-diphenylbenzene-1,4-diamine)]或N4,N4'-二(萘-1-基)-N4,N4’-二苯联苯基-4,4'-二胺[N4,N4'-di(naphthalen-1-yl)-N4,N4’-diphenylbiphenyl-4,4'-diamine，NPB]所制成。
所述第一和第二电洞注入层可由聚苯胺(polyaniline)或聚乙烯基二氧噻吩(polyethylenedioxythiophene)所制成，但不限于上述。
所述发光层可由发光材料制成，该发光材料包括主发光体(host)和掺杂物(dopant)，其中主发光体的材料例如9-[4-(1-萘基)苯基]-10-(2-萘基)蒽[9-(4-(naphthalen-1-yl)phenyl)-10-(naphthalen-2-yl)anthracene]，但不限于此。
针对红光OLED，发光层中的掺杂物(dopant)可以为具有苝配位基(peryleneligands)、荧蒽配位基(fluoranthene ligands)或二茚并配位基(periflantheneligands)的二价铱有机金属化合物，但不限于此。针对绿光OLED，发光层中的掺杂物可以为二氨基芴(diaminofluorenes)、蒽二胺(diaminoanthracenes)或具有苯基吡啶配位基(phenylpyridine ligands)的二价铱有机金属化合物，但不限于此。针对蓝光OLED，发光层中的掺杂物可以为二氨基芴、蒽二胺、芘二胺(diaminopyrenes)或具有苯基吡啶配位基的二价铱有机金属化合物，但不限于此。藉由不同的主发光体材料，OLED可发出红光、绿光或蓝光。
所述电子注入层可以电子注入材料制成，例如8-氧代萘-1-基锂[(8-oxidonaphthalen-1-yl)lithium(II)]，但不限于此。
所述第一电极可以为氧化铟锡电极(indium-doped tin oxide electrode)，但不限于上述。
所述第二电极的功函数(work function)低于第一电极的功函数。因此，第二电极可以是但不局限于铝电极、铟电极或镁电极。
本发明的其他目的、功效和技术特征，会以图、实施例和比较例进行更详细的说明。
附图说明
图1为OLED的侧视剖面图。
图2至图28分别为化合物I至XXVII的氢核磁共振光谱图。
具体实施方式
以下列举数种实施例作为示例说明本发明的化合物及其有机电子装置的实施方式，以突显本发明相较于现有技术的差异；本领域技术人员可通过本说明书的内容轻易了解本发明所能达成的优点与功效，并且于不背离本发明的精神下进行各种修饰与变更，以施行或应用本发明的内容。
中间物A1的合成
中间物A1(Intermediate A1)用于制备一种新颖化合物，中间物A1可通过下述合成机制A1中的步骤进行合成。
Figure BDA0001488987340000251
步骤1：合成中间物A1-1
混合86克(1.0当量)的3-溴二苯并[a,d]环庚烯-5-酮(3-bromodibenzo[a,d]cyclohepten-5-one)、106克(2.0当量)的N-溴代丁二酰亚胺(N-bromosuccinimide，NBS)和0.7克(0.01当量)的过氧化苯甲酰(benzyl peroxide)于起始材料5倍体积的四氯化碳(carbon tetrachloride，CCl4)中，并加热至85℃进行反应，在反应的过程中以高效液相层析仪(high performance liquid chromatography，HPLC)进行监测；当反应完成后，过滤分离反应产生的沉淀物，并以甲醇冲洗再以再结晶的方式纯化，接着经浓缩和干燥后，获得123克的白色固体产物，产率为92.3％。
经场脱附质谱(field desorption mass spectroscopy，FD-MS)分析确定，白色固体产物即为中间物A1-1。FD-MS分析结果：C15H9Br3O，理论值444.94，检测值444.94。
步骤2：合成中间物A1-2
秤取116.0克(1.0当量)的中间物A1-1，使中间物A1-1和呋喃(furan，1.5当量)溶解于四氢呋喃(tetrahydrofuran，THF，1.0M)中，降温至0℃，再加入87.8克(3.0当量)的叔丁醇钾(potassium tert-butoxide，K-OtBu)后于0℃下搅拌1小时，另接续于室温下再搅拌12小时。在反应进行后，以去离子水急速冷却并以溶剂萃取得有机层，再以硫酸钠达到除水的目的，接着通过减压蒸馏法去除有机层中的溶剂，并以硅胶管柱层析纯化获得纯化产物，纯化产物经浓缩和干燥后可获得淡黄色固体产物，产率为60.3％。
经FD-MS分析确定，淡黄色固体产物即为中间物A1-2。FD-MS分析结果：C19H11BrO2，理论值351.19，检测值为351.19。
步骤3：合成中间物A1-3
将1.0当量的中间物A1-2悬浮液和0.025当量、5％的钯碳催化剂(palladium oncarbon，Pd/C)于2.0M的乙酸乙酯(ethyl acetate，EA)中混合，并在氢气气球提供的氢气环境下搅拌3至6小时；接着，反应后的混合产物以硅藻土层过滤并以EA洗净，并使滤液在减压环境下进行浓缩，最后获得100克的黄色固体产物，产率为100％。
经FD-MS分析确定，黄色固体产物即为中间物A1-3。FD-MS分析结果：C19H13BrO2，理论值为353.21，检测值为353.21，中间物A1-3不需进一步纯化即可直接使用于接下来的步骤。
步骤4：合成中间物A1-4
1.0当量的中间物A1-3和2.0当量的对甲苯磺酸(p-toluenesulfonic acid，PTSA)在530毫升的甲苯中加热回流12小时，形成反应混合液；待反应混合液降至室温后，以碳酸氢钠饱和水溶液急速冷却反应混合液，再以二氯甲烷萃取获得有机层，并水洗有机层、使有机层浸泡于无水硫酸钠中干燥获得产物溶液，在减压环境下浓缩产物溶液，并以二氯甲烷和己烷体积比为1：1的洗提液于硅胶管柱中层析纯化，最后获得46克的淡黄色固体产物，产率为91.5％。
经FD-MS分析确定，淡黄色固体产物即为中间物A1-4。FD-MS分析结果：C19H11BrO，理论值335.19，检测值为335.19。
中间物A2的合成
中间物A2用于制备一种新颖化合物，中间物A2是以类似于合成中间物A1的步骤1至步骤4所合成，其差异在于起始物3-溴二苯并[a,d]环庚烯-5-酮以2-溴二苯并[a,d]环庚烯-5-酮(CAS No.198707-82-3)代替，中间物A2的合成路径统整于合成机制A2中，在合成机制A2中所有中间物的分析方法皆同前述，分析结果列于下表1。
Figure BDA0001488987340000271
中间物A3的合成
中间物A3用于制备一种新颖化合物，中间物A3是以类似于合成中间物A1的步骤1至步骤4所合成，其差异在于起始物3-溴二苯并[a,d]环庚烯-5-酮以3,7-二溴二苯并[a,d]环庚烯-5-酮(3,7-dibromodibenzo[a,d]cyclohepten-5-one)(CAS No.226946-20-9)代替，中间物A3的合成路径统整于合成机制A3中，在合成机制A3中所有中间物的分析方法皆同前述，分析结果列于下表1。
Figure BDA0001488987340000272
表1：中间物的化学结构式、产率、分子式与以FD-MS分析所得质量。
Figure BDA0001488987340000281
中间物A1至A3的修饰
除了中间物A1至A3之外，本领域技术人员可更替合成机制A1至A3中的起始物，并以类似于合成机制A1至A3的合成路径合成出其他中间物，例如以下列出的中间物A4至A15：
Figure BDA0001488987340000291
中间物B1至B6的合成
中间物B1至B6是以1-溴-2-碘苯(1-bromo-2-iodobenzene)与杂芳基硼酸反应而得，杂芳基硼酸为“反应物An(Reactant An)”，中间物B的合成路径如合成机制Bn所示。在合成机制B中，反应物An选自下表2中反应物A1至A6，“中间物Bn(Intermediate Bn)”选自于包括前述中间物B1至B6的群组。
Figure BDA0001488987340000292
根据合成机制B，中间物B1至B6根据以下步骤进行合成：将水和甲苯置于圆底烧瓶中形成混合液，并装设通有氩气的冷凝器于圆底烧瓶上，通过通以氩气使混合液搅动混合。接着，将1.5当量的碳酸钾、1当量的1-溴-2碘苯、1.2当量的反应物An、3当量的碳酸钾、200毫升的甲苯、0.06当量的三苯基膦(triphenylphosphine，PPh3)和0.015当量的乙酸钯于70℃的油浴下加热搅拌反应5小时形成反应混合液，当反应完成后，使混合液冷却至室温后，通过饱和食盐水和EA萃取获得有机层并以硫酸镁除水，接着以硅胶过滤，再将滤物以己烷洗涤并过滤获得中间物Bn。在合成机制B中所有中间物Bn的分析方法皆同前述，分析结果列于下表2。
表2：用于制备中间物B1至B6的反应物An的化学结构式，中间物B1至B6的化学结构式、产率、分子式和以FD-MS分析所得质量。
Figure BDA0001488987340000301
中间物B1至B6的修饰
除了中间物B1至B6之外，本领域技术人员可以其他二卤代苯(dihalobenzene)代替1-溴-2碘苯，亦可以其他杂芳基硼酸代替反应物A1至A6，再通过类似于合成机制B的合成路径合成出其他中间物Bn，举例来说，根据上述方法可合成出类似于中间物B1至B6的中间物B7和B8，如下所示：
Figure BDA0001488987340000311
中间物C的合成
前述中间物B1至B8(尤其是中间物B1至B6)可另用于合成中间物Cn，中间物Cn的合成路径如合成机制C1所示。在合成机制C1中，“中间物An”可以是任一选自于中间物A1至A15或其相似的中间物，“中间物Bn”可以是任一选自于中间物B1至B8或其相似的中间物，“中间物Cn”可以是任一选自于表3-1中所示的中间物C1至C9或其相似的中间物。中间物C1至C9分别以下述步骤所合成。
Figure BDA0001488987340000312
步骤1：醇中间物的合成
1.0当量的中间物Bn溶于120毫升的无水THF(0.4M)，降温至-78℃后缓慢加入正丁基锂(n-butyllithium，n-BuLi)(2.5M，1.0eq)形成反应溶液并搅拌1小时。接着，将中间物An(0.7eq)加入反应溶液中于室温下再搅拌3小时，待反应完成后，以饱和氯化铵水溶液冷却该反应溶液，再以有机溶剂萃取使有机相分离，于浓缩后使用石油醚再结晶以获得白色固体产物。
该白色产物以FD-MS分析确定为醇中间物，以中间物C1-1为例，FD-MS的分析结果为如下，分子式：C37H23BrO2，理论分子量：579.48，实际分子量：579.48。
该醇中间物不需另外纯化即可直接使用于步骤2。并对不同中间物An和中间物Bn合成的所有醇中间物以FD-MS进行分析确定，所使用的各中间物An、中间物Bn和醇中间物的化学结构式列于表3-1。
步骤2：中间物Cn的合成
混合1当量的醇中间物、醋酸(相较于反应物，w/v＝1/3)和5滴硫酸并在110℃下搅拌6小时，接着于低压环境下去除溶剂，于管柱层析纯化后以甲苯再结晶最后获得白色固体产物。
该固体产物经FD-MS进行分析确定，各中间物C1至C9的化学结构式、产率、分子式和质量列于表3-1。
表3-1：合成中间物C1至C9使用的中间物An和Bn；醇中间物的化学结构式；中间物C1至C9的化学结构式、产率、分子式和以FD-MS测得的质量。
Figure BDA0001488987340000321
Figure BDA0001488987340000331
Figure BDA0001488987340000341
中间物C1至C9的修饰
除了前述中间物C1至C9，本领域技术人员可采用其他有别于中间物A1至A3的中间物An以及/或有别于中间物B1至B6的中间物Bn，通过类似于反应机制C1合成路径合成出其他中间物Cn。本发明的中间物C1至C9的可适当修饰为下列的中间物C10至C33，但并非仅限于下方的例子：
Figure BDA0001488987340000351
Figure BDA0001488987340000361
前述中间物C6至C9和C22至C33可再进一步被氧化合成出其他中间物Cn，以中间物C6和C7为例，中间物C6和C7可分别通过合成机制C2和C3被氧化成中间物C34和C35。
中间物C34的合成
Figure BDA0001488987340000362
将30％、1.52毫升的过氧化氢水溶液在0℃的温度下逐滴加入75毫升的三氟乙酸中形成三氟过氧乙酸(trifluoroperacetic acid，TFA)溶液，并于滴加完成后移除冰浴，接着于搅拌的状态下将中间物C6(5g、1.0eq)缓慢加入三氟过氧乙酸溶液中，反应完成后以水洗涤反应物溶液并于过滤后获得固体，接着，将粗产物以硅胶管柱层析获得3.3克、产率为62.5％的中间物C34，以FD-MS分析确定其分子式为：C37H21BrO2S，理论分子量：609.53，测量分子量：609.53。
中间物C35的合成
Figure BDA0001488987340000371
中间物C35是以类似于中间物C34的方式合成，其差异在于，中间物C6以中间物C7替代。固体产物以FD-MS分析确定为中间物C35，产率为85％，FD-MS分析结果：分子式为C37H21BrO2S，理论分子量为609.53，测量分子量为609.53。
中间物C34和C35的修饰
除了中间物C34和C35之外，所属技术领域可选用具噻吩基的中间物Cn(例如中间物C8、C9、C22至C33)，并以类似于合成机制C2或C3的步骤来合成其他中间物Cn，例如下列中间物C36至C46：
Figure BDA0001488987340000372
Figure BDA0001488987340000381
中间物Cn-B的合成
前述中间物Cn可通过Miyaura硼基化反应(Miyaura borylation reaction)进一步修饰为中间物Cn-B，“中间物Cn-B”是将中间物Cn的溴基取代为频那醇硼基[(pinacolato)boron group]，中间物Cn-B可通过下述合成机制C1-B中的合成路径合成。
Figure BDA0001488987340000382
1.2当量的联硼酸频那醇酯[bis(pinacolato)diboron]、1.0当量的中间物Cn、0.015当量的[1,1-双(二苯基膦基)二茂铁]二氯化钯[1,1-bis(diphenylphosphino)-ferrocenedichloropalladium(II)，PdCl2(dppf)]和3.0当量的醋酸钾于在0.3M的无水1,4-二恶烷(1,4-dioxane)中形成的混合溶液，并在110℃的氮气环境下搅拌8小时，待冷却至室温后，于低压环境下去除溶剂，并将残余物以管柱层析纯化获得白黄色产物。该白黄色产物以FD-MS分析的结果列于表3-2中。
表3-2：合成中间物Cn-B使用的中间物Cn以及中间物Cn-B的化学结构式、产率、分子式和以FD-MS分析而得的质量。
Figure BDA0001488987340000383
Figure BDA0001488987340000391
Figure BDA0001488987340000401
中间物Cn-B的修饰
除了上述中间物Cn-B之外，本领域技术人员可任选自前述中间物Cn所构成的群组，并以类似于合成机制C1-B的方式对任一中间物Cn进行Miyaura硼基化反应，以合成中间物Cn-B如下所示：
Figure BDA0001488987340000402
新颖化合物的合成
各中间物Cn以及中间物Cn-B可分别与不同的反应物合成出新颖化合物，新颖化合物可通过下述合成机制I中的步骤进行合成。合成机制I中，“反应物B”选自于表4中包括反应物B1至B34的群组；“中间物C”选自于前述包括中间物Cn、中间物Cn-B及其相似物构成的群组。
Figure BDA0001488987340000411
表4：反应物B1至B34的化学结构式和CAS编号。
Figure BDA0001488987340000412
Figure BDA0001488987340000421
1.0当量的中间物Cn、0.01当量的醋酸钯、0.04当量的2-(二环己基磷基)联苯[dicyclohexylphosphine(2-biphenyl)，P(Cy)2(2-biPh)]、甲苯/乙醇(0.5M、v/v＝10/1)、3.0M的碳酸钾水溶液和1.2当量的反应物Bn形成的混合液于氮气环境下在100℃的温度下回流12小时，反应完全后，将水和甲苯加入反应物溶液中，接着，使用溶剂将有机相萃取出来并以硫酸钠干燥，于低压环境下使溶剂挥发后利用硅胶管柱层析纯化剩余物，并以甲苯再结晶获得新颖化合物。
用以合成化合物I至XXVII的反应物Bn和中间物Cn列于表5中，各化合物I至XXVII分别以氢核磁共振光谱仪(H1-NMR)和FD-MS分析确定，化合物I至XXVII的氢核磁共振光谱图如依序为图2至图28，且化合物I至XXVII的化学结构式、产率、分子式和质量列于表5中。
表5：合成化合物I至XXVII使用的反应物Bn和中间物Cn以及化合物I至XXVII的化学结构式、产率、分子式和以FD-MS分析而得的质量。
Figure BDA0001488987340000431
Figure BDA0001488987340000441
Figure BDA0001488987340000451
Figure BDA0001488987340000461
Figure BDA0001488987340000471
Figure BDA0001488987340000481
化合物I至XXVII的修饰
除了前述化合物I至XXVII之外，本领域技术人员可更替不同的中间物C(即中间物Cn或Cn-B)和反应物Bn，并以类似于合成机制I的合成路径合成出其他新颖化合物。
OLED装置的制备
将涂布有
Figure BDA0001488987340000482
厚ITO层的玻璃基板(以下简称为ITO基板)置于含有洗洁剂(厂牌：Fischer Co.)的蒸馏水(以Millipore Co.公司的滤器过滤二次而得的蒸馏水)中，并以超声波震荡30分钟；更换蒸馏水后再以超声波震荡10分钟以洗净ITO基板，并重复上述洗净步骤一次；洗净后，将前述玻璃基板以异丙醇、丙酮和甲醇以超声波震荡洗净，并使之干燥；接着，将玻璃基板置于电浆表面清洁机内，并以氧电浆清洁玻璃基板5分钟，再将清洁后的玻璃基板置于真空蒸镀机内。
之后，将真空蒸镀机的真空度维持在1x10-6torr至3x10-7torr，并于ITO基板上依序沉积各种有机材料和金属材料，并获得实施例1至19的OLED装置。于此，该ITO基板上依序沉积有第一电洞注入层(HIL-1)、第二电洞注入层(HIL-2)、第一电洞传输层(HTL-1)、第二电洞传输层(HTL-2)、蓝/绿/红发光层(BEL/GEL/REL)、电子传输层(ETL)、电子注入层(EIL)和阴极(Cthd)。
在上述OLED装置的各层中，HAT是用于形成HIL-1的材料和作为HIL-2中的掺杂物；HI-2是用于形成HIL-2的材料；HT-1和HT-2分别是用于形成HTL-1和HTL-2的材料；传统的ET和本发明的新颖化合物是用于形成ETL的材料；Liq是用于形成EIL的材料和作为ETL中的掺杂物；RH/GH/BH分别为形成REL/GEL/BEL的主要材料；RD/GD/BD可作为REL/GEL/BEL的掺杂物。实施例的OLED装置和比较例的OLED装置的主要差异为：比较例的OLED装置中ETL是以BCP制成，实施例的OELD装置中ETL是以列于表5的新颖化合物所制成。上述各化合物的详细化学结构式列于表6。
表6：使用于OLED装置中商业材料的化学结构式。
Figure BDA0001488987340000491
红光OLED装置的制备
红光OLED装置包括复数有机层，各有机层依序沉积于ITO基板上，各有机层的材料和厚度分别列于表7中。
表7：红光OLED装置中各有机层的涂布顺序、名称、材料和厚度。
Figure BDA0001488987340000492
Figure BDA0001488987340000501
绿光OLED装置的制备
绿光OLED装置包括复数有机层，该等有机层依序沉积于ITO基板上，各有机层的材料和厚度分别列于表8中。
表8：绿光OLED装置中各有机层的涂布顺序、名称、材料和厚度。
Figure BDA0001488987340000502
蓝光OLED装置的制备
蓝光OLED装置包括复数有机层，该等有机层依序沉积于ITO基板上，各有机层的材料和厚度分别列于表9中。
表9：蓝光OLED装置中各有机层的涂布顺序、名称、材料和厚度。
Figure BDA0001488987340000503
OLED装置的效能
为了评估OLED装置的效能，分别将红光(R)、绿光(G)和蓝光(B)的OLED装置连接于电源供应器(厂牌：Keithley；型号：2400)，并以PR650的亮度计检测，所测得的色度以为国际照明委员会(Commission Internationale de L’Eclairage 1931，CIE)制定的色度坐标[color coordinate(x,y)]示之，检测结果列于下表10中。其中，蓝光和红光的OLED装置是在1000尼特(1nit＝1cd/m2)的亮度下检测；绿光的OLED装置是在3000尼特的亮度下检测。
实施例1至19和比较例1至3中OLED装置的ETL材料、颜色和CIE数据、驱动电压、电流效率和外部量子效率(external quantum efficiency，EQE)列于下表10中。
表10：实施例1至19和比较例1至3中OLED装置的ETL材料、颜色、CIE、驱动电压、电流效率和外部量子效率。
Figure BDA0001488987340000511
根据表10的结果，相较于用于商业上OLED的材料(BCP)，本发明通过添加化合物I至XXVII于电子传输层中，可降低红光、绿光或蓝光OLED装置的驱动电压并改善电流效率和外部量子效率，证实本发明的新颖化合物适用添加于各色OLED装置中，并可达到降低驱动电压和改善电流效率的功效。
上述实施例仅为说明本发明的示例，并非于任何方面限制本发明所主张的范围，本领域技术人员能根据本发明的精神针对例如取代基的数量、位置或排列加以调整。本发明所主张的范围自应以申请范围所述为准，而非仅限于上述具体实施例。

Claims (20)

1.一种化合物，其如下式(I-I)至(I-XVIII)所示：
Figure FDA0003221327780000011
Figure FDA0003221327780000021
其中，Z1至Z8中至少一者是选自于由下列所构成的群组：氰基、硝基、环上碳数为6至60的芳香基、
Figure FDA0003221327780000022
Figure FDA0003221327780000031
其中，R1至R4分别独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、环上碳数为6的芳香基；
其中n为0；m为0至3的正整数；o是0；
其中，Z1至Z8中其余者及Z9至Z12各自独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为2至40的烯基、碳数为2至40的炔基、环上碳数为6至60的芳香基。
2.如权利要求1所述的化合物，其中该式(I-I)至(I-XVIII)中Z2、Z3、Z6和Z7中至少一者是选自于由下列所构成的群组：
Figure FDA0003221327780000032
Figure FDA0003221327780000041
其中，R1至R4分别独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、环上碳数为6的芳香基；
其中n为0；m为0至3的正整数；o是0；
该式(I-I)至(I-XVIII)中Z1、Z4、Z5和Z8分别独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为2的烯基和碳数为2的炔基。
3.如权利要求1所述的化合物，其中该式(I-I)至(I-XVIII)中Z9至Z12分别独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为2的烯基和碳数为2的炔基所构成的群组。
4.一种化合物，其如下式(I-I)至(I-XVIII)所示：
Figure FDA0003221327780000042
Figure FDA0003221327780000051
Figure FDA0003221327780000061
其中该式(I-I)至(I-XVIII)中Z2、Z3、Z6和Z7中至少一者是选自于由下列所构成的群组：
Figure FDA0003221327780000062
其中，Z1至Z8中其余者及Z9至Z12各自独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为2至40的烯基、碳数为2至40的炔基、环上碳数为6至60的芳香基。
5.一种化合物，其中该化合物选自于由下列所构成的群组：
Figure FDA0003221327780000063
Figure FDA0003221327780000071
Figure FDA0003221327780000081
6.一种化合物，其如下式(I-I)至(I-XVIII)所示：
Figure FDA0003221327780000082
Figure FDA0003221327780000091
Figure FDA0003221327780000101
其中，Z1至Z8中至少一者是选自于由下列所构成的群组：
Figure FDA0003221327780000102
其中，R1至R7分别独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为2至12的烯基、碳数为2至12的炔基、环上碳数为3至30的环烷基、环上碳数为6至30的芳香基、环上碳数为3至20的杂芳基；
其中n为0至4的正整数；m为0至3的正整数；o是0至3的正整数；m和o的总和小于或等于5；
其中，Z1至Z8中其余者及Z9至Z12各自独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为2至40的烯基、碳数为2至40的炔基、环上碳数为6至60的芳香基。
7.如权利要求6所述的化合物，其中该式(I-I)至(I-XVIII)中Z2、Z3、Z6和Z7中至少一者是选自于由下列所构成的群组：
Figure FDA0003221327780000111
其中，R1至R7分别独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为2至12的烯基、碳数为2至12的炔基、环上碳数为3至30的环烷基、环上碳数为6至30的芳香基、环上碳数为3至20的杂芳基；
其中n为0至4的正整数；m为0至3的正整数；o是0至3的正整数；m和o的总和小于或等于5；
该式(I-I)至(I-XVIII)中Z1、Z4、Z5和Z8分别独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为2至12的烯基和碳数为2至12的炔基。
8.如权利要求7所述的化合物，其中该式(I-I)至(I-XVIII)中Z2、Z3、Z6和Z7中至少一者是选自于由下列所构成的群组：
Figure FDA0003221327780000112
9.如权利要求6所述的化合物，其中该式(I-I)至(I-XVIII)中Z9至Z12分别独立选自于由下列所构成的群组：氢原子、氘原子、卤基、氰基、硝基、碳数为2至12的烯基和碳数为2至12的炔基所构成的群组。
10.一种化合物，其中该化合物选自于由下列所构成的群组：
Figure FDA0003221327780000121
11.一种有机电子装置，其包括第一电极、第二电极和设置于该第一电极和该第二电极间的有机层，其中该有机层包括如权利要求1至4中任一项所述的化合物。
12.如权利要求11所述的有机电子装置，其中该有机电子装置为有机发光二极管。
13.如权利要求12所述的有机电子装置，其中该有机发光二极管包括：
电洞注入层，其形成于该第一电极上；
电洞传输层，其形成于该电洞注入层上；
发光层，其形成于该电洞传输层上；
电子传输层，其形成于该发光层上，该有机层为该电子传输层；和
电子注入层，其形成于该电子传输层和该第二电极之间。
14.如权利要求12所述的有机电子装置，其中该有机发光二极管包括：
电洞注入层，其形成于该第一电极上；
电洞传输层，其形成于该电洞注入层上；
发光层，其形成于该电洞传输层上；
电洞阻挡层，其形成于该发光层上，该有机层为该电洞阻挡层；
电子传输层，其形成于该电洞阻挡层上；和
电子注入层，其形成于该电子传输层和该第二电极之间。
15.一种有机电子装置，其包括第一电极、第二电极和设置于该第一电极和该第二电极间的有机层，其中该有机层包括一化合物，该化合物选自于由下列所构成的群组：
Figure FDA0003221327780000131
Figure FDA0003221327780000141
Figure FDA0003221327780000151
16.一种有机电子装置，其包括第一电极、第二电极和设置于该第一电极和该第二电极间的有机层，其中该有机层包括如权利要求6至9中任一项所述的化合物。
17.如权利要求16所述的有机电子装置，其中该有机电子装置为有机发光二极管。
18.如权利要求17所述的有机电子装置，其中该有机发光二极管包括：
电洞注入层，其形成于该第一电极上；
电洞传输层，其形成于该电洞注入层上；
发光层，其形成于该电洞传输层上；
电子传输层，其形成于该发光层上，该有机层为该电子传输层；和
电子注入层，其形成于该电子传输层和该第二电极之间。
19.如权利要求17所述的有机电子装置，其中该有机发光二极管包括：
电洞注入层，其形成于该第一电极上；
电洞传输层，其形成于该电洞注入层上；
发光层，其形成于该电洞传输层上；
电洞阻挡层，其形成于该发光层上，该有机层为该电洞阻挡层；
电子传输层，其形成于该电洞阻挡层上；和
电子注入层，其形成于该电子传输层和该第二电极之间。
20.一种有机电子装置，其包括第一电极、第二电极和设置于该第一电极和该第二电极间的有机层，其中该有机层包括一化合物，该化合物选自于由下列所构成的群组：
Figure FDA0003221327780000161
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