CN108164496B - 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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CN108164496B
CN108164496B CN201711274180.2A CN201711274180A CN108164496B CN 108164496 B CN108164496 B CN 108164496B CN 201711274180 A CN201711274180 A CN 201711274180A CN 108164496 B CN108164496 B CN 108164496B
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CN108164496A (zh
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吴蕙玲
廖良玓
谢淑珠
陈济中
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ANQING FEIKAI NEW MATERIAL Co.,Ltd.
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Shanghai Nichem Fine Chemical Co Ltd
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Abstract

本发明关于化合物及其有机电子装置，所述化合物如下式(I)所示：
Figure DDA0001496175140000011
式(I)；其中Y是氧原子、硫原子或是二氧化硫基，X1和X2分别独立为C(Ra)，该二(Ra)彼此相同或不同，该二(Ra)相互连接形成第一芳香环；X3和X4分别独立为C(Rb)，该二(Rb)彼此相同或不同，该二(Rb)相互连接形成第二芳香环或杂芳环。

Description

化合物及其有机电子装置
技术领域
本发明涉及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)、3-(联苯-4-基)-5-(4-叔丁基苯基)-4-苯基-4H-1,2,4-三唑(3-(Biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole，TAZ)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 GDA0002340429660000021
式(I)中，Y是氧原子、硫原子或是二氧化硫基，X1和X2分别独立为C(Ra)，该二(Ra)彼此相同或不同，该二(Ra)相互连接形成第一芳香环；X3和X4分别独立为C(Rb)，该二(Rb)彼此相同或不同，该二(Rb)相互连接形成第二芳香环或杂芳环。
式(I)中，Z1至Z12分别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、环上碳数为6至60的芳硅基、碳数为1至40的硼烷基、环上碳数为6至60的芳硼基、碳数为1至40的膦基和碳数为1至40的氧膦基。
根据本发明，式(I)中X1和X2之间的双键以及该二(Ra)间的键相互共轭并构成该第一芳香环；相似的，式(I)中X3和X4之间的双键以及该二(Rb)间的键相互共轭并构成该第二芳香环或该杂芳环。
较佳的，式(I)中自X1和X2延伸形成的第一芳香环以及式(I)中自X3和X4延伸形成的第二芳香环各自独立为经取代或未经取代且碳数为6至60的碳环，更佳的，该第一芳香环和该第二芳香环各自独立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的碳环可以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(naphthalene ring)、经取代或未经取代的蒽环(anthracenering)、经取代或未经取代的菲环(phenanthrene ring)、经取代或未经取代的芘环(pyrenering)、经取代或未经取代的荧蒽环(fluoranthene ring)、经取代和未经取代的苯并荧蒽环(benzofluoranthene ring)和经取代或未经取代的芴环(fluorene ring)，但不限于此。较佳的，该碳数为6至20的碳环上的取代基可以是但不限于卤基、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，式(I)中自X3和X4延伸形成的杂芳环可以包含至少一呋喃基(furangroup)或至少一噻吩基(thiophene group)。例如，所述杂芳环可以是但不限于：经取代或未经取代的二苯基呋喃环(dibenzofuran ring)、经取代或未经取代的二苯基噻吩环(dibenzothiophene ring)、经取代或未经取代的二苯并噻吩砜环(dibenzothiophenesulfone ring)、经取代或未经取代的苯并呋喃环(benzofuran ring)、经取代或未经取代的异苯并呋喃环(isobenzofuran ring)、经取代或未经取代的苯并噻吩环(benzothiophene ring)或经取代或未经取代的异苯并噻吩环(isobenzothiophenering)。
较佳的，Z1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、碳数环上为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，当Y是氧原子时，所述化合物可以下述任一通式表示，例如：
Figure GDA0002340429660000041
Figure GDA0002340429660000051
当Y是硫原子时，所述化合物可以下述任一通式表示，例如：
Figure GDA0002340429660000052
Figure GDA0002340429660000061
当Y是二氧化硫基时，所述化合物可以下述任一通式表示，例如：
Figure GDA0002340429660000062
Figure GDA0002340429660000071
根据本发明，前述A1和A2分别独立为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，所述芳香结构包含在由所述第二芳香环或所述杂芳环中。
根据本发明，前述各Z13是选自于由下列所构成的群组：甲基、乙基、丙基、丁基、戊基、己基和苯基。
较佳的，该二(Rc)相互连接形成的芳香结构可以是经取代或未经取代且碳数为6至20的芳香环状结构；例如但不仅限于：经取代或未经取代的苯环结构、经取代或未经取代的萘环结构、经取代或未经取代的蒽环结构、经取代或未经取代的菲环结构、经取代或未经取代的芘环结构、经取代或未经取代的荧蒽环结构、经取代或未经取代的苯并荧蒽环结构或经取代或未经取代的芴环结构；所述经取代或未经取代且碳数为6至20的芳香环状结构上的取代基可以是：卤基、氰基、硝基、三氟甲基、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，上述任一通式中Z1至Z8中的至少一者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、具有至少一官能基且环上碳数为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。上述任一通式中Z1至Z8中的其他者可以是氢原子、氘原子或说明书中提到的其余取代基；所述官能基选自于由氰基、硝基、氟基和氯基所构成的群组。
更佳的，上述任一通式中Z1至Z8中的至少一者是特定芳香取代基，该特定芳香取代基是选自于由下列所构成的群组：
Figure GDA0002340429660000081
Figure GDA0002340429660000091
Figure GDA0002340429660000101
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、三氟甲基、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的整数；m为0至3的整数；o是0至3的整数；m和o的总和小于或等于5。
较佳的，R1至R3分别独立为苯基、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。
于其中一实施例，上述任一通式中Z1至Z8中至少一者为
Figure GDA0002340429660000102
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。
于另一实施例，上述任一通式中Z1至Z8中至少一者为
Figure GDA0002340429660000103
其中，R2可以是吡啶基或苯氰基(cyanophenyl)，R1和R3可以是上述的任一取代基。
较佳的，上述任一通式中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三嗪基(triazine group)。
较佳的，上述任一通式中Z1、Z2、Z3、Z6、Z7和Z8中至少一者是选自于上述特定芳香取代基，而Z4和Z5各自独立选自于由氢原子、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的炔基所构成的群组。或者，上述任一通式中Z2、Z3、Z6和Z7中至少一者是选自于上述特定芳香取代基，而Z1、Z4、Z5和Z8各自独立选自于由氢原子、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的炔基所构成的群组。
较佳的，上述任一通式中Z2、Z3、Z6和Z7中至少一者是选自于由下列所构成的群组：
Figure GDA0002340429660000111
较佳的，上述任一通式中Z1、Z2、Z3、Z6、Z7和Z8中至少一者是前述特定芳香取代基，，而Z4和Z5各自独立选自于由氢原子、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的炔基所构成的群组。
较佳的，上述任一通式中的Z9至Z12可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Z1和Z8可以是相同或是不同；根据本发明，Z2和Z7可以是相同或是不同；根据本发明，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。
例如，Z1、Z4至Z8各自独立为氢原子或氘原子，Z2和/或Z3可以是该特定的芳香取代基；或者，Z1、Z2、Z4、Z5、Z7和Z8各自独立为氢原子或氘原子，且Z3和Z6皆为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 GDA0002340429660000121
Figure GDA0002340429660000131
Figure GDA0002340429660000141
Figure GDA0002340429660000151
Figure GDA0002340429660000161
Figure GDA0002340429660000171
Figure GDA0002340429660000181
Figure GDA0002340429660000191
Figure GDA0002340429660000201
Figure GDA0002340429660000211
Figure GDA0002340429660000221
Figure GDA0002340429660000231
Figure GDA0002340429660000241
Figure GDA0002340429660000251
Figure GDA0002340429660000261
Figure GDA0002340429660000271
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CCCIV)所制成，本发明的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包括一电洞阻挡层，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包括一电子阻挡层，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。通过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27分别为化合物I至XXVI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例示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 GDA0002340429660000291
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溶解于960毫升、浓度为1.0M的四氢呋喃(tetrahydrofuran，THF)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)于浓度为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
53g、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 GDA0002340429660000311
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 GDA0002340429660000321
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 GDA0002340429660000322
Figure GDA0002340429660000331
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 GDA0002340429660000332
中间物B1至B4的合成
中间物B1至B4是以1-氟-2-硝基苯(1-fluoro-2-nitrobenzene)与苯酚衍生物(Ar1-OH，即反应物An)反应而得，中间物Bn的合成路径如合成机制B-1所示。在合成机制B-1中，“反应物An(Reactant An)”选自表2-1中反应物A1至A4中的任一者，“中间物Bn(Intermediate Bn)”选自于包括前述中间物B1至B4的群组中的任一者。
Figure GDA0002340429660000341
根据合成机制B-1，所述中间物B1至B4是依以下步骤1至3所合成。
步骤1：中间物Bn-1的合成
将1.0当量的苯酚衍生物(Ar1-OH，反应物An)、50克(1当量)的1-氟-2-硝基苯和230.9克(2当量)的碳酸铯(Cs2CO3)混合于2080毫升的0.17体积摩尔浓度(M)的二甲基甲酰胺(DMF)中，并于90℃的氩气环境下搅拌，再以水冷却、醋酸乙酯萃取、硫酸镁干燥再接续于过滤后在低压环境下浓缩，将粗产物以硅胶管柱层析纯化，以FD-MS分析确定为中间物Bn-1；以B1-1为例，FD-MS的分析结果为C12H9NO3，理论分子量为215.2，测量分子量为215.2。
步骤2：中间物Bn-2的合成
将1.0当量的中间物Bn-1和10克的5％的钯碳催化剂(Pd/C、0.015当量)加入680毫升、0.5M的乙醇中于70℃下搅拌，将31.6克(2.0当量)的水合肼(hydrazine monohydrate)缓慢加入溶液中，待反应完成后以硅藻土垫过滤并于低压环境下浓缩获得产物，所述产物经FD-MS分析确定为中间物Bn-2。以B1-2为例，FD-MS的分析结果为C12H11NO，理论分子量为185.22，测量分子量为185.22。
步骤3：中间物Bn的合成
将1.0当量的中间物Bn-2和172.5克(3.0当量)的对甲苯磺酸水合物(PTSA*H2O)混合于224毫升的1.3M的乙腈(ACN)溶液中以冰浴降温至5℃，将41.7克(2当量)的亚硝酸钠(NaNO2)溶于240毫升水中并逐滴加入，于滴加完成后继续维持5℃的冰浴1小时，将反应完的重氮盐水溶液以溶有100g(2当量)碘化钾(KI)的300毫升水溶液处理，接着，以醋酸乙酯萃取，在合并有机相后以10％亚硫酸钠水溶液洗涤并以硫酸钠干燥，再于低压环境下过滤获得粗产物，粗产物经过硅胶管柱层析纯化后获得中间物Bn。用以合成中间物Bn(即中间物B1至B4)的Ar1-OH的化学结构式以及由步骤1至3合成的产物(即中间物Bn-1、Bn-2和Bn)的化学结构式与产率列于表2-1中，中间物B1至B4皆以FD-MS分析确定，并将分析结果列于表2-1中。
表2-1：用以合成中间物B1至B4的反应物An以及中间物B1至B4的化学结构式、产率和以FD-MS分析的分子式与质量。
Figure GDA0002340429660000351
中间物B5和B6的合成
与中间物B1至B4不同，中间物B5和B6是由2-溴苯硫酚(2-bromobenznenthiol)和芳基碘衍生物(aryl iodide，以I-Ar1表示，即反应物An)反应合成，因此，中间物Bn可以另一个合成机制B-2来合成，在合成机制B-2中，“反应物An”可以是表2-2中的反应物A5、A6或其相似物，“中间物Bn”可以是中间物B5或B6。
Figure GDA0002340429660000361
根据合成机制B-2，0.5％当量的三(二亚苄基丙酮)二钯(tris(dibenzylideneacetone)dipalladium，Pd2(dba)3)、0.01当量的二(2-二苯基邻苯基)醚(Bis(2-diphenylphosphinophenyl)ether，DPEphos)、1.5当量的叔丁醇钠(sodium tert-butoxide，Na-OtBu)加入螺口小瓶中、接着将甲苯(toluene)和搅拌子加入所述螺口小瓶，再加入1.05当量的2-溴苯硫酚和1.0当量的芳基碘衍生物(反应物An)；再密封所述螺口小瓶后于100℃加热搅拌1小时获得粗产物，再将粗产物以硅藻土垫过滤后浓缩，接着以庚烷作为洗提液于一短硅胶管柱中纯化而获得中间物Bn。
用以合成中间物Bn(尤其指中间物B5和B6)的I-Ar1的化学结构式以及中间物Bn(即中间物B5和B6)的化学结构式与产率列于表2-2中，中间物B5和B6皆以FD-MS分析确定，并以将分析结果列于表2-2中。
表2-2：用以合成中间物B5和B6的反应物An以及中间物B5和B6的化学结构式、产率和以FD-MS分析的分子式与质量。
Figure GDA0002340429660000362
中间物B1至B4的修饰。
除了中间物B1至B4之外，本领域技术人员可选用任何除了1-氟-2-硝基苯的卤基硝基苯(halonitrobenzene)以及除了反应物A1至A4外的其余苯酚衍生物作为反应物，并以类似于合成机制B-1的步骤来合成其他中间物Bn，例如下列中间物B7至B18：
Figure GDA0002340429660000371
中间物B5和B6的修饰
除了中间物B5和B6之外，本领域技术人员可选用任何除了2-溴苯硫酚的卤苯硫酚(halobenzenethiol)以及除了反应物A5和A6外的其余芳基碘衍生物作为反应物An，并以类似于合成机制B-2的步骤来合成其他中间物Bn，例如下列中间物B19至B34：
Figure GDA0002340429660000372
Figure GDA0002340429660000381
中间物Cn的合成
前述中间物B1至B34(Intermediate Bn)，尤其是中间物B1至B6，可进一步用于合成中间物Cn(Intermediate Cn)，中间物Cn的合成路径如合成机制C-1所示。在合成机制C-1中，“中间物An”(Intermediate An)选自于包括中间物A1至A15及其相似物的群组中的任一者，“中间物Bn”选自于包括中间物B1至B34及其相似物的群组中的任一者，“中间物Cn”选自于表3-1中包括中间物C1至C12及其相似物的群组中的任一者；中间物C1至C12分别以下述步骤所合成。
Figure GDA0002340429660000382
步骤1：醇中间物Cn-1的合成
1.0当量的中间物Bn溶于120毫升的0.4M的无水四氢呋喃(THF)，降温至-78℃后缓慢加入正丁基锂(n-butyllithium，n-BuLi)(2.5M，1.0当量)形成反应溶液并搅拌1小时。接着，将中间物An(0.7当量)加入反应溶液中于25℃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。
所述白色固体产物经FD-MS进行分析确定，各中间物Cn-1的化学结构式、产率以及经FD-MS分析确定的分子式和质量列于表3-1。
步骤2：中间物Cn的合成
混合1当量的中间物Cn-1、醋酸(HOAc)(相较于反应物，w/v＝1/3)和5滴硫酸(H2SO4)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。
所述固体产物经FD-MS进行分析确定，各中间物C1至C12的化学结构式、产率以及经FD-MS分析确定的分子式和质量列于表3-1。
表3-1：合成中间物C1至C10使用的中间物An和Bn；中间物Cn-1的化学结构式；中间物Cn的化学结构式和产率与以FD-MS测得的质量和分子式。
Figure GDA0002340429660000391
Figure GDA0002340429660000401
Figure GDA0002340429660000411
中间物C13的合成
前述中间物C9至C12可再进一步氧化成其他中间物Cn，以中间物C9为例，中间物C9可通过合成机制C-2氧化成中间物C13。
Figure GDA0002340429660000421
将中间物C9(20g,1.0eq)和30％、7.0当量的过氧化氢溶于250毫升的醋酸中，加热至100℃于氮气的环境下反应8小时，反应完成后，以水洗涤反应溶液并过滤获得粗产物，在使粗产物经硅胶管柱层析纯化后获得中间物C13，产率为85.3％。
该固体产物经FD-MS分析确定为中间物C13，以FD-MS分析的分子式为：C31H19BrO2S，理论分子量：535.45，测量分子量：535.45。
中间物C14的合成
中间物C14是根据合成机制C-3以类似于中间物C13的合成方式合成，其差异在于中间物C9以中间物C10替代。
Figure GDA0002340429660000422
中间物C1至C12的修饰
除了中间物C1至C12之外，所属技术领域可选用任何除了中间物A1至A3外的中间物An和任何除了中间物B1至B6外的中间物Bn，根据合成机制C-1来合成中间物Cn，例如下列中间物C15至C46：
Figure GDA0002340429660000431
Figure GDA0002340429660000441
中间物C13和C14的修饰
除了中间物C13和C14之外，所属技术领域可选用其他中间物Cn，例如中间物C9至C12和中间物C31至C46，并根据合成机制C-2或合成机制C-3来合成其他中间物Cn，例如下列中间物C47至C58：
Figure GDA0002340429660000442
Figure GDA0002340429660000451
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 GDA0002340429660000452
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)-ferrocene dichloropalladium(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。
该白黄色产物即为中间物Cn-B，中间物Cn-B的化学结构式和产率以及FD-MS分析的分子式和质量结果列于表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的化学结构式和产率以FD-MS分析而得的分子式和质量。
Figure GDA0002340429660000461
Figure GDA0002340429660000471
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。
新颖化合物的合成
各中间物Cn和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 GDA0002340429660000481
表4：反应物B1至B34的化学结构式和CAS编号。
Figure GDA0002340429660000482
Figure GDA0002340429660000491
Figure GDA0002340429660000501
1.0当量的中间物Cn或CnB、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2.1当量的反应物B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XXVI的反应物B和中间物Cn或Cn-B列于表5中，各化合物I至XXVI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XXVI的氢核磁共振光谱图如依序为图2至图27，且化合物I至XXVI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XXVI使用的反应物Bn和中间物Cn以及化合物I至XXVI的化学结构式、产率、分子式和以FD-MS分析而得的质量。
Figure GDA0002340429660000502
Figure GDA0002340429660000511
Figure GDA0002340429660000521
Figure GDA0002340429660000531
Figure GDA0002340429660000541
Figure GDA0002340429660000551
化合物I至XXVI的修饰
除了前述化合物I至XXVI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B，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 GDA0002340429660000552
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，并以超音波震荡30分钟；更换蒸馏水后再以超音波震荡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、丙酮和甲醇以超音波震荡洗净，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1x10-6 torr至3x10-7 torr，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33和比较例1至3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的掺杂物；HI-2是用于形成HIL-2；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；Liq是用于形成EIL的材料和作为ETL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 GDA0002340429660000561
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 GDA0002340429660000571
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 GDA0002340429660000572
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 GDA0002340429660000573
OLED装置的效能
为了评估OLED装置的效能，分别将红光、绿光和蓝光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[colorcoordinate(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33和比较例1至3中OLED装置的ETL材料、CIE颜色、驱动电压、电流效率和外部量子效率(external quantum efficiency，EQE)列于表10中。
表10：实施例1至33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EQE。
Figure GDA0002340429660000581
Figure GDA0002340429660000591
根据表10的结果，相较于用于商业上OLED的材料，本发明通过添加化合物I至XXVI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电流效率，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、改善电流效率和改善外部电流效率的功效。
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 (11)

1.一种化合物，其如下式(I)所示：
Figure FDA0002340429650000011
其中，X1和X2分别独立为C(Ra)，该二(Ra)彼此相同或不同，该二(Ra)相互连接形成第一芳香环；X3和X4分别独立为C(Rb)，该二(Rb)彼此相同或不同，该二(Rb)相互连接形成第二芳香环或杂芳环；Y是氧原子、硫原子或是二氧化硫基；
该Z2、Z3、Z6和Z7中的至少一者选自于由下列所构成的群组：
Figure FDA0002340429650000012
Figure FDA0002340429650000021
该Z2、Z3、Z6和Z7中的其余者和Z1、Z4、Z5和Z8和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、三氟甲基、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、环上碳数为6至60的芳硅基、碳数为1至40的硼烷基、环上碳数为6至60的芳硼基、碳数为1至40的膦基和碳数为1至40的氧膦基。
2.如权利要求1所述的化合物，其中该化合物以下式(I-I)至式(I-XXXIII)表示：
Figure FDA0002340429650000022
Figure FDA0002340429650000031
Figure FDA0002340429650000041
Figure FDA0002340429650000051
其中，A1和A2分别独立为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该第二芳香环或该杂芳环中；
其中，各Z13是选自于由下列所构成的群组：甲基、乙基、丙基、丁基、戊基、己基和苯基。
3.如权利要求2所述的化合物，其中该自A1和A2延伸形成的芳香结构是选自于由下列所构成的群组：经取代或未经取代的苯环结构、经取代或未经取代的萘环结构、经取代或未经取代的蒽环结构、经取代或未经取代的菲环结构、经取代或未经取代的芘环结构、经取代或未经取代的荧蒽环结构、经取代和未经取代的苯并荧蒽环结构和经取代或未经取代的芴环结构。
4.如权利要求1至3中任一项所述的化合物，其中该自X1和X2延伸形成的第一芳香环是选自于由下列所构成的群组：经取代或未经取代的苯环结构、经取代或未经取代的萘环结构、经取代或未经取代的蒽环结构、经取代或未经取代的菲环结构、经取代或未经取代的芘环结构、经取代或未经取代的荧蒽环结构、经取代或未经取代的苯并荧蒽环结构和经取代或未经取代的芴环结构。
5.如权利要求1至3中任一项所述的化合物，其中该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。
6.如权利要求1所述的化合物，其中该化合物是选自于由下列所构成的群组：
Figure FDA0002340429650000061
Figure FDA0002340429650000071
7.一种有机电子装置，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6中任一项所述的化合物。
8.如权利要求7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。
9.如权利要求8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。
10.如权利要求8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。
11.如权利要求7所述的有机电子装置，其中该化合物选自于由下列所构成的群组：
Figure FDA0002340429650000081
Figure FDA0002340429650000091
Figure FDA0002340429650000101
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TWI662013B (zh) * 2016-03-24 2019-06-11 大陸商上海嶸彩光電材料有限公司 化合物及其有機電子裝置

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