CN113402498A - 螺二芴化合物、制剂、有机发光器件及显示或照明装置 - Google Patents

螺二芴化合物、制剂、有机发光器件及显示或照明装置 Download PDF

Info

Publication number
CN113402498A
CN113402498A CN202110951753.0A CN202110951753A CN113402498A CN 113402498 A CN113402498 A CN 113402498A CN 202110951753 A CN202110951753 A CN 202110951753A CN 113402498 A CN113402498 A CN 113402498A
Authority
CN
China
Prior art keywords
substituted
unsubstituted
compound
spirobifluorene
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110951753.0A
Other languages
English (en)
Other versions
CN113402498B (zh
Inventor
王子兴
申屠晓波
廖张程
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Huadisplay Optoelectronics Co Ltd
Original Assignee
Zhejiang Huadisplay Optoelectronics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Huadisplay Optoelectronics Co Ltd filed Critical Zhejiang Huadisplay Optoelectronics Co Ltd
Priority to CN202110951753.0A priority Critical patent/CN113402498B/zh
Publication of CN113402498A publication Critical patent/CN113402498A/zh
Application granted granted Critical
Publication of CN113402498B publication Critical patent/CN113402498B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本发明公开了螺二芴化合物、制剂、有机发光器件及显示或照明装置，其中，该螺二芴化合物的结构如下列式（I）或式（II）所示：
Figure 100004_DEST_PATH_IMAGE001
Figure 100004_DEST_PATH_IMAGE002
本发明的螺二芴化合物具有较好的热稳定性，且将该螺二芴化合物用于有机发光器件，提高了器件的效率，降低了驱动电压，且使用寿命有所明显提升，具有很好的应用前景。

Description

螺二芴化合物、制剂、有机发光器件及显示或照明装置
技术领域
本发明涉及一种螺二芴化合物，尤其涉及一种螺二芴化合物、制剂、有机发光器件及显示或照明装置，属于有机电致发光领域。
背景技术
有机发光器件(OLED器件)具有视角广阔、响应速度快、色彩质量高、可实现柔性发光等优点，其具有广阔的应用前景。 常见的OLED器件通常包括以下种类的有机材料：空穴注入材料、空穴传输材料、电子传输材料以及各色的发光材料(染料或者掺杂客体材料)和相应的主体材料等。通常，空穴传输材料的电子迁移速率比电子传输材料的电子迁移速率高出两个数量级。因此，为了使电子和空穴在发光层能够很好地复合形成激子并发光，通常在制作有机发光器件中采用空穴阻挡层阻止空穴到达电子传输层。空穴阻挡材料应具有较低的HOMO能级、更高的电子迁移速率、更高的三线态能级及较高的氧化电位和较宽的带隙，以提高其电子的传输能力及空穴和激子的阻挡能力，使激子限制在发光层中，减少光能量的损失，从而大大提高有机发光器件的效率。
很多有机材料能够有效地传输空穴，因此，为了提高有机发光器件的发光效率，在很多情况下，往往在阴极一侧额外加一层电子传输/空穴阻挡层，以阻挡空穴传输，从而将载流子复合限制在发光层区域。
因此，有必要开发高三重态能级空穴阻挡材料(Hole-blocking layer, HBL)或电子传输材料，这样，一方面增加电子与空穴在发光层中的复合几率，减少光能量的损失，大大提高了器件效率；另一方面，高三重态能级有利于使用高效率磷光或TADF材料。
发明内容
为了克服现有的有机电子传输材料/空穴阻挡材料中存在的问题，本发明的目的是提供一种螺二芴化合物，该螺二芴化合物具有提高的电子传输能力及空穴和激子的阻挡能力，使激子限制在发光层中，减少能量的损失，从而进一步提高了有机发光器件的效率和寿命，且降低了操作电压。
为了实现本发明的目的，本发明的技术方案如下：
本发明提供了螺二芴化合物，其中，其结构式如下列式（I）或式（II）所示：
Figure 769686DEST_PATH_IMAGE001
Figure 587469DEST_PATH_IMAGE002
。
其中，Ar1和Ar2各自独立地选自取代或未取代的C6-C30的芳基、取代或未取代的C2-C30的杂芳基。
R选自H、D、卤素、取代或未取代的C1~C40的烷基、取代或未取代的C1~C40的烷氧基、取代或未取代的C1~C40的环烷基、取代或未取代的C1~C40的杂烷基、取代或未取代的C6~C40的芳基、取代或未取代的C1~C40的杂芳基、取代或未取代的C1~C60的硅基、取代或未取代的C6~C60的芳族稠环或取代或未取代的C1~C60的杂芳族稠环，n为0至10的整数。
优选地，本发明的螺二芴化合物选自由以下组成的群组：
Figure 648966DEST_PATH_IMAGE003
Figure 651426DEST_PATH_IMAGE004
Figure 736057DEST_PATH_IMAGE005
Figure 951006DEST_PATH_IMAGE006
Figure 804693DEST_PATH_IMAGE007
Figure 994366DEST_PATH_IMAGE008
Figure 81139DEST_PATH_IMAGE009
Figure 116091DEST_PATH_IMAGE010
Figure 73552DEST_PATH_IMAGE011
Figure 434126DEST_PATH_IMAGE012
Figure 290087DEST_PATH_IMAGE013
Figure 315680DEST_PATH_IMAGE014
Figure 206276DEST_PATH_IMAGE015
Figure 675434DEST_PATH_IMAGE016
Figure 471221DEST_PATH_IMAGE017
Figure 379134DEST_PATH_IMAGE018
。
其中，Ar1和Ar2各自独立地选自取代或未取代的C6-C30的芳基、取代或未取代的C2-C30的杂芳基。
R选自H、D、卤素、取代或未取代的C1~C40的烷基、取代或未取代的C1~C40的烷氧基、取代或未取代的C1~C40的环烷基、取代或未取代的C1~C40的杂烷基、取代或未取代的C6~C40的芳基、取代或未取代的C1~C40的杂芳基、取代或未取代的C1~C60的硅基、取代或未取代的C6~C60的芳族稠环或取代或未取代的C1~C60的杂芳族稠环，n为0至10的整数。
更优选地，本发明的螺二芴化合物的结构式中R选自由以下组成的群组：
Figure 576766DEST_PATH_IMAGE019
Figure 13564DEST_PATH_IMAGE020
Figure 781800DEST_PATH_IMAGE021
Figure 211513DEST_PATH_IMAGE022
Figure 279963DEST_PATH_IMAGE023
Figure 340192DEST_PATH_IMAGE024
Figure 392461DEST_PATH_IMAGE025
Figure 579860DEST_PATH_IMAGE026
Figure 548822DEST_PATH_IMAGE027
Figure 530685DEST_PATH_IMAGE028
Figure 335830DEST_PATH_IMAGE029
Figure 334045DEST_PATH_IMAGE030
Figure 908246DEST_PATH_IMAGE031
Figure 310277DEST_PATH_IMAGE032
Figure 337139DEST_PATH_IMAGE033
Figure 866341DEST_PATH_IMAGE034
Figure 747578DEST_PATH_IMAGE035
Figure 133560DEST_PATH_IMAGE036
Figure 100248DEST_PATH_IMAGE037
Figure 229878DEST_PATH_IMAGE038
Figure 450775DEST_PATH_IMAGE039
Figure 522505DEST_PATH_IMAGE040
Figure 461642DEST_PATH_IMAGE041
Figure 129384DEST_PATH_IMAGE042
Figure 719634DEST_PATH_IMAGE043
Figure 712998DEST_PATH_IMAGE044
。
其中，上述结构中未被氘代的基团，可以被部分或全部氘代。
更优选地，本发明的螺二芴化合物的结构式中Ar1和Ar2各自独立地选自由以下组成的群组：
Figure 123119DEST_PATH_IMAGE045
Figure 860131DEST_PATH_IMAGE046
Figure 55620DEST_PATH_IMAGE047
Figure 203574DEST_PATH_IMAGE048
Figure 117303DEST_PATH_IMAGE049
Figure 392426DEST_PATH_IMAGE050
Figure 957269DEST_PATH_IMAGE051
Figure 230118DEST_PATH_IMAGE052
Figure 5045DEST_PATH_IMAGE053
Figure 83860DEST_PATH_IMAGE054
Figure 503209DEST_PATH_IMAGE055
Figure 743697DEST_PATH_IMAGE056
Figure 632019DEST_PATH_IMAGE057
Figure 498212DEST_PATH_IMAGE058
Figure 522800DEST_PATH_IMAGE059
Figure 934190DEST_PATH_IMAGE060
Figure 293496DEST_PATH_IMAGE061
Figure 714113DEST_PATH_IMAGE062
Figure 842475DEST_PATH_IMAGE063
Figure 893607DEST_PATH_IMAGE064
。
其中，上述结构中未被氘代的基团，可以被部分或全部氘代。
更优选地，本发明的螺二芴化合物选自由以下组成的群组：
Figure 553259DEST_PATH_IMAGE065
Figure 698938DEST_PATH_IMAGE066
Figure 760435DEST_PATH_IMAGE067
Figure 966158DEST_PATH_IMAGE068
Figure 847526DEST_PATH_IMAGE069
Figure 547629DEST_PATH_IMAGE070
Figure 712900DEST_PATH_IMAGE071
Figure 840256DEST_PATH_IMAGE072
Figure 474499DEST_PATH_IMAGE073
Figure 961981DEST_PATH_IMAGE074
Figure 732491DEST_PATH_IMAGE075
Figure 280016DEST_PATH_IMAGE076
Figure 135977DEST_PATH_IMAGE077
Figure 177882DEST_PATH_IMAGE078
Figure 317745DEST_PATH_IMAGE079
Figure 786904DEST_PATH_IMAGE080
Figure 130160DEST_PATH_IMAGE081
Figure 225024DEST_PATH_IMAGE082
Figure 704547DEST_PATH_IMAGE083
Figure 859454DEST_PATH_IMAGE084
Figure 627690DEST_PATH_IMAGE085
Figure 73714DEST_PATH_IMAGE086
Figure 125853DEST_PATH_IMAGE087
Figure 733552DEST_PATH_IMAGE088
Figure 785821DEST_PATH_IMAGE089
Figure 488067DEST_PATH_IMAGE090
Figure 145445DEST_PATH_IMAGE091
Figure 438892DEST_PATH_IMAGE092
Figure 916140DEST_PATH_IMAGE093
Figure 703968DEST_PATH_IMAGE094
Figure 730699DEST_PATH_IMAGE095
Figure 883462DEST_PATH_IMAGE096
Figure 159592DEST_PATH_IMAGE097
Figure 485531DEST_PATH_IMAGE098
Figure 383080DEST_PATH_IMAGE099
Figure 221592DEST_PATH_IMAGE100
Figure 673433DEST_PATH_IMAGE101
Figure 52330DEST_PATH_IMAGE102
Figure 538806DEST_PATH_IMAGE103
Figure 95690DEST_PATH_IMAGE104
Figure 80832DEST_PATH_IMAGE105
Figure 951836DEST_PATH_IMAGE106
Figure 355136DEST_PATH_IMAGE107
Figure 269871DEST_PATH_IMAGE108
Figure 758621DEST_PATH_IMAGE109
Figure 971600DEST_PATH_IMAGE110
Figure 167089DEST_PATH_IMAGE111
Figure 65775DEST_PATH_IMAGE112
Figure 228772DEST_PATH_IMAGE113
Figure 503896DEST_PATH_IMAGE114
Figure 803159DEST_PATH_IMAGE115
Figure 138325DEST_PATH_IMAGE116
Figure 273772DEST_PATH_IMAGE117
Figure 601854DEST_PATH_IMAGE118
Figure 506356DEST_PATH_IMAGE119
Figure 12423DEST_PATH_IMAGE120
Figure 884433DEST_PATH_IMAGE121
Figure 501359DEST_PATH_IMAGE122
Figure 775215DEST_PATH_IMAGE123
Figure 452184DEST_PATH_IMAGE124
Figure 562222DEST_PATH_IMAGE125
Figure 232107DEST_PATH_IMAGE126
Figure 111201DEST_PATH_IMAGE127
Figure 959072DEST_PATH_IMAGE128
Figure 805674DEST_PATH_IMAGE129
Figure 764402DEST_PATH_IMAGE130
Figure 12850DEST_PATH_IMAGE131
Figure 766042DEST_PATH_IMAGE132
Figure 116252DEST_PATH_IMAGE133
Figure 65623DEST_PATH_IMAGE134
Figure 981626DEST_PATH_IMAGE135
Figure 358250DEST_PATH_IMAGE136
Figure 726914DEST_PATH_IMAGE137
Figure 965128DEST_PATH_IMAGE138
Figure 250485DEST_PATH_IMAGE139
Figure 548742DEST_PATH_IMAGE140
Figure 404703DEST_PATH_IMAGE141
Figure 695876DEST_PATH_IMAGE142
Figure 586471DEST_PATH_IMAGE143
Figure 304898DEST_PATH_IMAGE144
Figure 648154DEST_PATH_IMAGE145
Figure 228171DEST_PATH_IMAGE146
Figure 425803DEST_PATH_IMAGE147
Figure 128180DEST_PATH_IMAGE148
Figure 411263DEST_PATH_IMAGE149
Figure 794971DEST_PATH_IMAGE150
Figure 394579DEST_PATH_IMAGE151
Figure 454808DEST_PATH_IMAGE152
Figure 772657DEST_PATH_IMAGE153
Figure 209323DEST_PATH_IMAGE154
Figure 663438DEST_PATH_IMAGE155
Figure 645301DEST_PATH_IMAGE156
Figure 699714DEST_PATH_IMAGE157
Figure 425224DEST_PATH_IMAGE158
Figure 451955DEST_PATH_IMAGE159
Figure 870298DEST_PATH_IMAGE160
Figure 162739DEST_PATH_IMAGE161
Figure 675629DEST_PATH_IMAGE162
Figure 104336DEST_PATH_IMAGE163
Figure 942848DEST_PATH_IMAGE164
Figure 925847DEST_PATH_IMAGE165
Figure 242428DEST_PATH_IMAGE166
Figure 791221DEST_PATH_IMAGE167
Figure 285787DEST_PATH_IMAGE168
Figure 536509DEST_PATH_IMAGE169
Figure 407513DEST_PATH_IMAGE170
Figure 810813DEST_PATH_IMAGE171
Figure 725548DEST_PATH_IMAGE172
Figure 214298DEST_PATH_IMAGE173
Figure 138261DEST_PATH_IMAGE174
Figure 333750DEST_PATH_IMAGE175
Figure 498015DEST_PATH_IMAGE176
Figure 661012DEST_PATH_IMAGE177
Figure 670556DEST_PATH_IMAGE178
Figure 235398DEST_PATH_IMAGE179
Figure 304986DEST_PATH_IMAGE180
Figure 706011DEST_PATH_IMAGE181
Figure 971776DEST_PATH_IMAGE182
Figure 204174DEST_PATH_IMAGE183
Figure 897193DEST_PATH_IMAGE184
Figure 582252DEST_PATH_IMAGE185
Figure 136861DEST_PATH_IMAGE186
Figure 473034DEST_PATH_IMAGE187
Figure 87686DEST_PATH_IMAGE188
Figure 712571DEST_PATH_IMAGE189
Figure 867609DEST_PATH_IMAGE190
Figure 12282DEST_PATH_IMAGE191
Figure 132858DEST_PATH_IMAGE192
Figure 730192DEST_PATH_IMAGE193
Figure 688921DEST_PATH_IMAGE194
Figure 671789DEST_PATH_IMAGE195
Figure 690561DEST_PATH_IMAGE196
Figure 24459DEST_PATH_IMAGE197
Figure 990141DEST_PATH_IMAGE198
Figure 358674DEST_PATH_IMAGE199
Figure 17189DEST_PATH_IMAGE200
Figure 651433DEST_PATH_IMAGE201
Figure 404494DEST_PATH_IMAGE202
Figure 378266DEST_PATH_IMAGE203
Figure 207682DEST_PATH_IMAGE204
Figure 578489DEST_PATH_IMAGE205
Figure 620394DEST_PATH_IMAGE206
Figure 245411DEST_PATH_IMAGE207
Figure 963837DEST_PATH_IMAGE208
Figure 307094DEST_PATH_IMAGE209
Figure 667537DEST_PATH_IMAGE210
Figure 147060DEST_PATH_IMAGE211
Figure 787120DEST_PATH_IMAGE212
Figure 866940DEST_PATH_IMAGE213
Figure 250648DEST_PATH_IMAGE214
Figure 850256DEST_PATH_IMAGE215
Figure 176064DEST_PATH_IMAGE216
Figure 431596DEST_PATH_IMAGE217
Figure 665000DEST_PATH_IMAGE218
Figure 587957DEST_PATH_IMAGE219
Figure 819087DEST_PATH_IMAGE220
Figure 358653DEST_PATH_IMAGE221
Figure 146480DEST_PATH_IMAGE222
Figure 173211DEST_PATH_IMAGE223
Figure 122712DEST_PATH_IMAGE224
Figure 352837DEST_PATH_IMAGE225
Figure 928043DEST_PATH_IMAGE226
Figure 560013DEST_PATH_IMAGE227
Figure 132946DEST_PATH_IMAGE228
Figure 647104DEST_PATH_IMAGE229
Figure 979996DEST_PATH_IMAGE230
Figure 246898DEST_PATH_IMAGE231
Figure 272623DEST_PATH_IMAGE232
Figure 8498DEST_PATH_IMAGE233
Figure 394349DEST_PATH_IMAGE234
Figure 532069DEST_PATH_IMAGE235
Figure 712383DEST_PATH_IMAGE236
Figure 201134DEST_PATH_IMAGE237
Figure 610249DEST_PATH_IMAGE238
Figure 117323DEST_PATH_IMAGE239
Figure 219271DEST_PATH_IMAGE240
Figure 929738DEST_PATH_IMAGE241
Figure 391812DEST_PATH_IMAGE242
Figure 504125DEST_PATH_IMAGE243
Figure 573712DEST_PATH_IMAGE244
Figure 489584DEST_PATH_IMAGE245
Figure 240503DEST_PATH_IMAGE246
Figure 456589DEST_PATH_IMAGE247
Figure 900340DEST_PATH_IMAGE248
Figure 585399DEST_PATH_IMAGE249
Figure 654855DEST_PATH_IMAGE250
Figure 741760DEST_PATH_IMAGE251
Figure 605680DEST_PATH_IMAGE252
Figure 778035DEST_PATH_IMAGE253
Figure 870756DEST_PATH_IMAGE254
Figure 327014DEST_PATH_IMAGE255
Figure 846988DEST_PATH_IMAGE256
Figure 506640DEST_PATH_IMAGE257
Figure 652319DEST_PATH_IMAGE258
Figure 713816DEST_PATH_IMAGE259
Figure 185117DEST_PATH_IMAGE260
Figure 269748DEST_PATH_IMAGE261
Figure 766588DEST_PATH_IMAGE262
Figure 869543DEST_PATH_IMAGE263
Figure 59215DEST_PATH_IMAGE264
Figure 880410DEST_PATH_IMAGE265
Figure 384203DEST_PATH_IMAGE266
。
本发明还提供了制剂，该制剂包含螺二芴化合物和至少一种溶剂，该溶剂可以是本领域技术人员公知的不饱和烃溶剂（例如甲苯、二甲苯、均三甲苯、四氢化萘、十氢萘、双环己烷、正丁基苯、仲丁基苯、叔丁基苯等）、卤化饱和烃溶剂（例如四氯化碳、氯仿、二氯甲烷、二氯乙烷、氯丁烷、溴丁烷、氯戊烷、溴戊烷、氯己烷、溴己烷、氯环己烷、溴环己烷等）、卤化不饱和烃溶剂（例如氯苯、二氯苯、三氯苯等）、醚类溶剂（例如四氢呋喃、四氢吡喃等）或酯类溶剂（例如苯甲酸烷基酯等）。
本发明还提供了有机发光器件，其包括阴极层、阳极层和有机功能层，该有机功能层为空穴注入层、空穴传输层、发光层、电子传输层和电子注入层中至少一层，其中，该有机功能层包含螺二芴化合物或制剂。本发明的有机发光器件的空穴传输层和电子传输层还包含一种或多种p型掺杂剂（如LiQ）。
优选地，该有机发光器件的发光层中含有本发明的螺二芴化合物和至少一种客体材料，其中，该螺二芴化合物与客体材料的体积比为1：99至99：1；该客体材料为荧光材料或磷光材料。
更优选地，该有机发光器件的发光层中含有所述的螺二芴化合物作为第一主体，另一种有机化合物作为第二主体，所述第一主体与第二主体的体积比为8：2至2：8。
优选地，该有机发光器件的电子传输层中含有本发明的螺二芴化合物；所述螺二芴化合物可以单独形成电子传输层，也可以和掺杂剂共同形成电子传输层；当电子传输层中含有掺杂剂时，所述螺二芴化合物与掺杂的体积比为2：8~8：2；所述掺杂剂为n型掺杂剂。
本发明的有机发光器件可以归类为顶发射、底发射或双面发射。本发明的螺二芴化合物同样可以应用于照明的OLED、柔性OLED等。
本发明还提供了显示或照明装置，其中，其包括上述的有机发光器件。
本发明的螺二芴化合物由于不对称的结构特征，将其应用于有机发光器件，提高了器件效率、寿命、成膜等性能，且本发明的螺二芴化合物由于具有较高的三线态能级，使能量传递更加充分，电子和空穴的传递更加平衡，从而在保持低操作电压的情况下，器件的效率和寿命更高。
本发明的螺二芴化合物的主要特点是同时引入了取代的三嗪基团和吡啶单元，意外地发现，本发明的螺二芴化合物具有以下显著效果：
（1）在吡啶环和取代三嗪基团的协同作用下，本发明的螺二芴化合物具有较高的玻璃化转变温度；
（2）与不具有吡啶基团的类似化合物相比（如芳基三嗪螺二芴化合物）相比，本发明的螺二芴化合物应用于有机发光器件，可以提高器件的效率和寿命；
（3）本发明的螺二芴化合物能够较好地平衡空穴和电子的传递，从而降低有机发光器件的操作电压；
附图说明
图1为本发明的有机发光器件的结构示意图，图2 本发明化合物12的差示量热扫描（DSC）曲线图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合具体实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明的OLED器件中含有空穴传输层，空穴传输材料可以选自已知的材料，特别优选地选自以下结构，但并不代表本发明限于以下结构：
Figure 154713DEST_PATH_IMAGE267
Figure 702238DEST_PATH_IMAGE268
Figure 823778DEST_PATH_IMAGE269
Figure 849372DEST_PATH_IMAGE270
Figure 739967DEST_PATH_IMAGE271
Figure 474705DEST_PATH_IMAGE272
Figure 801650DEST_PATH_IMAGE273
Figure 647246DEST_PATH_IMAGE274
Figure 680816DEST_PATH_IMAGE275
Figure 383193DEST_PATH_IMAGE276
Figure 151429DEST_PATH_IMAGE277
Figure 581142DEST_PATH_IMAGE278
Figure 384013DEST_PATH_IMAGE279
Figure 257291DEST_PATH_IMAGE280
Figure 762090DEST_PATH_IMAGE281
Figure 746227DEST_PATH_IMAGE282
Figure 918451DEST_PATH_IMAGE283
Figure 900313DEST_PATH_IMAGE284
Figure 439879DEST_PATH_IMAGE285
。
本发明的OLED器件中含有空穴传输层，其包含一种或多种p型掺杂剂。本发明优选的p型掺杂剂为以下结构，但并不代表本发明限于以下结构：
Figure 476974DEST_PATH_IMAGE286
Figure 254437DEST_PATH_IMAGE287
Figure 203939DEST_PATH_IMAGE288
Figure 417751DEST_PATH_IMAGE289
Figure 212532DEST_PATH_IMAGE290
Figure 890507DEST_PATH_IMAGE291
。
电子传输层可以选自参考化合物ET-1至 ET-6中一者或本发明所述的螺二芴化合物，但并不代表本发明限于以下结构：
Figure 214172DEST_PATH_IMAGE292
Figure 993909DEST_PATH_IMAGE293
Figure 310490DEST_PATH_IMAGE294
Figure 328124DEST_PATH_IMAGE295
Figure 150587DEST_PATH_IMAGE296
Figure 338992DEST_PATH_IMAGE297
。
电子传输层可以有机材料与一种或多种n型掺杂剂（如LiQ）共同形成。
发光层由BH-1作为主体，BD-1作为客体材料组成
Figure 6733DEST_PATH_IMAGE298
。
合成实施例
Figure 596984DEST_PATH_IMAGE299
Figure 793610DEST_PATH_IMAGE300
Figure 16781DEST_PATH_IMAGE301
Figure 940743DEST_PATH_IMAGE302
Figure 198549DEST_PATH_IMAGE303
Figure 284186DEST_PATH_IMAGE304
Figure 260232DEST_PATH_IMAGE305
Figure 473039DEST_PATH_IMAGE306
。
上述中间体1到中间体10是通过本领域公知的方法合成得到的。
Figure 834619DEST_PATH_IMAGE307
Figure 373047DEST_PATH_IMAGE308
Figure 305231DEST_PATH_IMAGE309
Figure 570997DEST_PATH_IMAGE310
Figure 803395DEST_PATH_IMAGE311
Figure 230834DEST_PATH_IMAGE312
Figure 181472DEST_PATH_IMAGE313
Figure 736082DEST_PATH_IMAGE314
Figure 72254DEST_PATH_IMAGE315
Figure 421327DEST_PATH_IMAGE316
Figure 328103DEST_PATH_IMAGE317
Figure 466829DEST_PATH_IMAGE318
Figure 345923DEST_PATH_IMAGE319
Figure 443061DEST_PATH_IMAGE320
Figure 40396DEST_PATH_IMAGE321
Figure 999125DEST_PATH_IMAGE322
Figure 247572DEST_PATH_IMAGE323
Figure 266344DEST_PATH_IMAGE324
Figure 334663DEST_PATH_IMAGE325
实施例1：化合物1的合成
在氮气保护下，于反应容器中装入中间体1 （10毫摩尔）、3,5-二苯基-1-氯三嗪（10毫摩尔）、甲苯：105毫升、乙醇：26毫升，接着，加入预先将碳酸钾：5克溶解于H2O：30毫升而成的水溶液，同时通入氮气。加入醋酸钯：0.1克，三苯基膦0.4克在加热回流下搅拌12小时。自然冷却后，分离出有机层，浓缩而得到粗产物。在将该粗产物用二氯甲烷/石油醚混合溶液作为淋洗剂，过硅胶柱得到白色固体，5.5克 （产率88%） ；1H NMR (400 MHz)：δ 7.21-7.54 (m, 13H), 7.75 (d, 1H), 7.81 (d,1H), 7.86-7.98 (m, 6H), 8.12-8.27 (m,5H), 8.55 (d, 1H), 8.68 (s, 1H), LC-MS: M/Z 实测625.2 (M+H)+，理论624.23。
实施例2：化合物2的合成
化合物2的合成步骤与化合物1类似，选用中间体2作为反应物，产率87%；1H NMR(400 MHz)：δ 7.26 (dd, 2H), 7.36-7.58 (m, 9H), 7.62 (d, 2H), 7.65 (d, 2H),7.79-7.82 (m, 3H), 7.86 (d, 2H), 8.01 (d, 1H), 8.12-8.27 (m, 5H), 8.63 (d,2H), LC-MS: M/Z 实测625.2 (M+H)+，理论624.23。
实施例3：化合物3的合成
化合物3的合成步骤与化合物1类似，选用中间体3作为反应物，产率85%；1H NMR(400 MHz)：δ 7.26 (dd, 2H), 7.46-7.58 (m, 7H), 7.60 (dd, 2H), 7.65 (d, 2H),7.70-7.78 (m, 3H), 7.92 (d, 2H), 8.11-8.33 (m, 8H), 8.62 (d, 1H), 8.71 (s,1H), LC-MS: M/Z 实测625.2 (M+H)+，理论624.23。
实施例4：化合物4的合成
化合物4的合成步骤与化合物1类似，选用中间体4作为反应物，产率82%；1H NMR(400 MHz)：δ 7.4 -7.62 (m, 16H), 7.80 (d, 2H), 7.85 (d, 2H), 8.21-8.37 (m,6H), 8.65 (d, 2H); LC-MS: M/Z 实测625.2 (M+H)+，理论624.23。
实施例5：化合物5的合成
化合物5的合成步骤与化合物1类似，选用中间体5作为反应物，产率82%；1H NMR(400 MHz)：δ 7.35 (dd, 1H), 7.46 -7.52 (m, 8H), 7.53 (dd, 1H), 7.65-7.82 (m,7H), 7.92 (d, 1H), 8.13-8.32 (m, 8H), 8.35 (d, 1H), 8.52-8.60 (m, 3H); LC-MS:M/Z 实测675.2 (M+H)+，理论674.25。
实施例6：化合物6的合成
化合物6的合成步骤与化合物1类似，选用中间体6作为反应物，产率82%；1H NMR(400 MHz)：δ 7.35 (dd, 1H), 7.46 -7.52 (m, 8H), 7.53 (dd, 1H), 7.65-7.82 (m,7H), 7.92 (d, 1H), 8.13-8.32 (m, 8H), 8.35 (d, 1H), 8.52-8.60 (m, 3H); LC-MS:M/Z 实测675.2 (M+H)+，理论674.25。
实施例7：化合物7的合成
化合物7的合成步骤与化合物1类似，选用中间体7作为反应物，产率77%；1H NMR(400 MHz)：δ 7.25 (dd, 1H), 7.41 -7.72 (m, 17H), 7.83 (d, 1H), 7.89 (d, 1H),8.13-8.25 (m, 4H), 8.33-8.42 (m, 3H), 8.57-8.66 (m, 3H); LC-MS: M/Z 实测675.2(M+H)+，理论674.25。
实施例8：化合物8的合成
化合物8的合成步骤与化合物1类似，选用中间体2作为反应物，产率79%；1H NMR(400 MHz)：δ 7.35 (dd, 1H), 7.40 -7.58 (m, 10H), 7.63 (d, 2H), 7.79 (d, 2H),7.73 (d, 2H),7.79-7.82 (m, 4H), 7.92 (d, 2H), 8.01-8.06 (m, 2H), 8.21-8.33(m, 4H), 8.36 (d, 1H), 8.69 (d, 2H); LC-MS: M/Z 实测715.2 (M+H)+，理论714.24。
实施例9：化合物9的合成
化合物9的合成步骤与化合物1类似，选用中间体3作为反应物，产率83%；LC-MS:M/Z 实测715.2 (M+H)+，理论714.24。
实施例10：化合物10的合成
化合物10的合成步骤与化合物1类似，选用中间体4作为反应物，产率75%；1H NMR(400 MHz)：δ 7.31(dd, 1H), 7.40 -7.68 (m, 16H), 7.75 (d, 2H), 7.99 (d, 2H),8.01-8.06 (m, 2H), 8.21-8.32 (m, 3H), 8.35 (s, 1H), 8.66 (d, 2H) , 8.70 (s,1H); LC-MS: M/Z 实测715.2 (M+H)+，理论714.24。
实施例11：化合物11的合成
化合物11的合成步骤与化合物1类似，选用中间体5作为反应物，产率81%；LC-MS:M/Z 实测765.2 (M+H)+，理论764.26。
实施例12：化合物12的合成
化合物12的合成步骤与化合物1类似，选用中间体7作为反应物，产率71%；1H NMR(400 MHz)：δ 7.23 (dd, 1H), 7.33 (dd, 1H), 7.42 -7.61 (m, 10H), 7.65-7.81 (m,7H), 7.83 (d, 2H), 7.91-8.03 (m, 3H), 8.19 (d, 1H), 8.26 (d, 2H), 8.33 (s,1H), 8.46 (d, 1H) , 8.56-8.72 (m, 4H); LC-MS: M/Z 实测765.2 (M+H)+，理论764.26；玻璃化转变温度Tg （162.5度）。
实施例13：化合物13的合成
化合物13的合成步骤与化合物1类似，选用中间体8作为反应物，产率87%；LC-MS:M/Z 实测715.2 (M+H)+，理论714.24。
实施例14：化合物14的合成
化合物14的合成步骤与化合物1类似，选用中间体4作为反应物，产率76%；LC-MS:M/Z 实测675.2(M+H)+，理论674.25。
实施例15：化合物15的合成
化合物15的合成步骤与化合物1类似，选用中间体4作为反应物，产率74%；1H NMR(400 MHz)：δ 7.30 (t, 1H), 7.38-7.71 (m, 22H), 7.71 (d, 1H), 7.85 (d, 1H),7.93-8.11 (m, 5H), 8.29 (d, 1H), 8.36 (s, 1H), 8.39 (s, 1H), 8.46 (d, 1H),8.69 (d, 2H), 8.92 (s, 1H)；LC-MS: M/Z 实测751.3(M+H)+，理论750.28。
实施例16：化合物16的合成
化合物16的合成步骤与化合物1类似，选用中间体4作为反应物，产率79%；LC-MS:M/Z 实测791.3(M+H)+，理论790.27。
实施例17：化合物17的合成
化合物17的合成步骤与化合物1类似，选用中间体7作为反应物，产率71%；LC-MS:M/Z 实测725.3(M+H)+，理论724.26。
实施例18：化合物18的合成
化合物18的合成步骤与化合物1类似，选用中间体9作为反应物，产率75%；LC-MS:M/Z 实测675.2(M+H)+，理论674.25。
实施例19：化合物19的合成
化合物19的合成步骤与化合物1类似，选用中间体10作为反应物，产率82%；LC-MS:M/Z实测751.3(M+H)+，理论750.28。
器件实施例
如图1所示，本发明的有机发光器件（底发射OLED器件）包括基板110、阳极120、空穴注入层130、空穴传输层140、发光层150、空穴阻挡层160、电子传输层170、电子注入层180和阴极190。本发明有机发光器件的各层可采用真空蒸镀、溅射、离子电镀等方法，或湿法成膜如旋涂、打印、印刷等方法形成，所用的溶剂没有特别限制。
器件例1-22的制造：
在发光面积为2 mm×2 mm大小的ITO玻璃的表面或阳极上将HT-1与P-3共蒸或者蒸镀HT-1形成10 nm的空穴注入层(HIL)（其中，HT-1与P-3的体积比为97:3），90 nm的空穴传输层(HTL)，接着在空穴传输层上蒸镀HT-10，形成厚度为10nm的电子阻挡层（EBL），随后在电子阻挡层上将主体化合物（BH-1）与客体化合物（BD-1）共蒸形成25nm的发光层(EML)(可含有本发明的化合物)（其中，BH-1与BD-1的体积比为97:3 ），最后用本发明的化合物1-19：LiQ (其中，本发明的化合物1-19与LiQ的体积比为1:1)形成电子传输层(ETL)35 nm，然后蒸镀阴极Al 40 nm，从而制造了有机发光元件。
对比器件1-6的制造：
对比器件1-6的制造与器件例1-22类似，区别仅在于在对比器件1-6中采用ET-1~ET-6（作为电子传输层材料）替代本发明的化合物1-19制备了相应的对比OLED器件。
本发明的OLED器件及对比器件1-6通过本领域公知的相同的标准方法表征。
表1显示了对比器件1-6及器件例1-19中有机发光器件的性能测试结果，其中，LT95寿命是以对比器件1的寿命为100%作为对比。
表1
Figure 97082DEST_PATH_IMAGE326
。
与对比器件1（电子传输层材料为ET-1）相比，对比器件2-3采用的电子传输材料为ET-2和ET-3，它们在蓝光OLED器件中具有较高的效率，同时也具有较长的使用寿命，分别是对比器件1的169%和120%，但是它们的操作电压较高，不满足发光器件对低能耗的要求，所以需要一类化合物，使用它后，有机发光器件的电压要与对比器件1持平或降低，效率和寿命均要比对比器件1有所提升。
对比器件4-6中，在具有三嗪取代的螺二芴体系中增加苯环取代，与对比器件2-3相比，器件的电压有所降低，但效率和使用寿命完全没有优势。在此基础上，本发明将吡啶基团引入到三嗪取代的螺二芴体系中，意外地发现，吡啶基团的引入(化合物1)后，器件例1的操作电压与对比器件1的持平，寿命略差，但电流效率得到提升。与吡啶并在螺二芴环上（对比器件2-3）相比，对比器件1中有机发光器件的电压下降比较明显，效率持平或略有提升，但寿命不如对比器件2-3。器件例1-19中的操作电压均比对比器件2~6低，且与对比器件1中器件的操作电压基本持平或略有降低，但器件的效率则得到了大幅度的提升，同时器件寿命也有显著的提升，比如器件例18中的器件，用化合物18作为电子传输层材料，该器件的操作电压下降0.1伏，该器件的电流效率提升10%，寿命提升20%。器件例12中的器件的效率提升8%，但寿命提升了32%。因此，本发明的螺二芴化合物由于同时具有吡啶和取代三嗪，因此，将其应用于有机发光器件，在降低操作电压的同时，从而提升了器件的效率和寿命。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (11)

1.螺二芴化合物，其结构式如下列式（I）或式（II）所示：
Figure DEST_PATH_IMAGE001
Figure DEST_PATH_IMAGE002
其中，Ar1和Ar2各自独立地选自取代或未取代的C6-C30的芳基、取代或未取代的C2-C30的杂芳基；
R选自H、D、卤素、取代或未取代的C1~C40的烷基、取代或未取代的C1~C40的烷氧基、取代或未取代的C1~C40的环烷基、取代或未取代的C1~C40的杂烷基、取代或未取代的C6~C40的芳基、取代或未取代的C1~C40的杂芳基、取代或未取代的C1~C60的硅基、取代或未取代的C6~C60的芳族稠环或取代或未取代的C1~C60的杂芳族稠环，n为0至10的整数。
2.根据权利要求1所述的螺二芴化合物，其中，所述化合物选自由以下组成的群组：
Figure DEST_PATH_IMAGE003
Figure DEST_PATH_IMAGE004
Figure DEST_PATH_IMAGE005
Figure DEST_PATH_IMAGE006
Figure DEST_PATH_IMAGE007
Figure DEST_PATH_IMAGE008
Figure DEST_PATH_IMAGE009
Figure DEST_PATH_IMAGE010
Figure DEST_PATH_IMAGE011
Figure DEST_PATH_IMAGE012
Figure DEST_PATH_IMAGE013
Figure DEST_PATH_IMAGE014
Figure DEST_PATH_IMAGE015
Figure DEST_PATH_IMAGE016
Figure DEST_PATH_IMAGE017
Figure DEST_PATH_IMAGE018
其中，Ar1和Ar2各自独立地选自取代或未取代的C6-C30的芳基、取代或未取代的C2-C30的杂芳基；
R选自H 、D、卤素、取代或未取代的C1~C40的烷基、取代或未取代的C1~C40的烷氧基、取代或未取代的C1~C40的环烷基、取代或未取代的C1~C40的杂烷基、取代或未取代的C6~C40的芳基、取代或未取代的C1~C40的杂芳基、取代或未取代的C1~C60的硅基、取代或未取代的C6~C60的芳族稠环或取代或未取代的C1~C60的杂芳族稠环，n为0至10的整数。
3.根据权利要求1或2所述的螺二芴化合物，其中，所述化合物中R选自由以下组成的群组：
Figure DEST_PATH_IMAGE019
Figure DEST_PATH_IMAGE020
Figure DEST_PATH_IMAGE021
Figure DEST_PATH_IMAGE022
Figure DEST_PATH_IMAGE023
Figure DEST_PATH_IMAGE024
Figure DEST_PATH_IMAGE025
Figure DEST_PATH_IMAGE026
Figure DEST_PATH_IMAGE027
Figure DEST_PATH_IMAGE028
Figure DEST_PATH_IMAGE029
Figure DEST_PATH_IMAGE030
Figure DEST_PATH_IMAGE031
Figure DEST_PATH_IMAGE032
Figure DEST_PATH_IMAGE033
Figure DEST_PATH_IMAGE034
Figure DEST_PATH_IMAGE035
Figure DEST_PATH_IMAGE036
Figure DEST_PATH_IMAGE037
Figure DEST_PATH_IMAGE038
Figure DEST_PATH_IMAGE039
Figure DEST_PATH_IMAGE040
Figure DEST_PATH_IMAGE041
Figure DEST_PATH_IMAGE042
Figure DEST_PATH_IMAGE043
Figure DEST_PATH_IMAGE044
其中，上述结构中未被氘代的基团，可以被部分或全部氘代。
4.根据权利要求1或2所述的螺二芴化合物，其中，所述化合物中Ar1和Ar2各自独立地选自由以下组成的群组：
Figure DEST_PATH_IMAGE045
Figure DEST_PATH_IMAGE046
Figure DEST_PATH_IMAGE047
Figure DEST_PATH_IMAGE048
Figure DEST_PATH_IMAGE049
Figure DEST_PATH_IMAGE050
Figure DEST_PATH_IMAGE051
Figure DEST_PATH_IMAGE052
Figure DEST_PATH_IMAGE053
Figure DEST_PATH_IMAGE054
Figure DEST_PATH_IMAGE055
Figure DEST_PATH_IMAGE056
Figure DEST_PATH_IMAGE057
Figure DEST_PATH_IMAGE058
Figure DEST_PATH_IMAGE059
Figure DEST_PATH_IMAGE060
Figure DEST_PATH_IMAGE061
Figure DEST_PATH_IMAGE062
Figure DEST_PATH_IMAGE063
Figure DEST_PATH_IMAGE064
其中，上述结构中未被氘代的基团，可以被部分或全部氘代。
5.根据权利要求1或2所述的螺二芴化合物，其中，所述化合物选自由以下组成的群组：
Figure DEST_PATH_IMAGE065
Figure DEST_PATH_IMAGE066
Figure DEST_PATH_IMAGE067
Figure DEST_PATH_IMAGE068
Figure DEST_PATH_IMAGE069
Figure DEST_PATH_IMAGE070
Figure DEST_PATH_IMAGE071
Figure DEST_PATH_IMAGE072
Figure DEST_PATH_IMAGE073
Figure DEST_PATH_IMAGE074
Figure DEST_PATH_IMAGE075
Figure DEST_PATH_IMAGE076
Figure DEST_PATH_IMAGE077
Figure DEST_PATH_IMAGE078
Figure DEST_PATH_IMAGE079
Figure DEST_PATH_IMAGE080
Figure DEST_PATH_IMAGE081
Figure DEST_PATH_IMAGE082
Figure DEST_PATH_IMAGE083
Figure DEST_PATH_IMAGE084
Figure DEST_PATH_IMAGE085
Figure DEST_PATH_IMAGE086
Figure DEST_PATH_IMAGE087
Figure DEST_PATH_IMAGE088
Figure DEST_PATH_IMAGE089
Figure DEST_PATH_IMAGE090
Figure DEST_PATH_IMAGE091
Figure DEST_PATH_IMAGE092
Figure DEST_PATH_IMAGE093
Figure DEST_PATH_IMAGE094
Figure DEST_PATH_IMAGE095
Figure DEST_PATH_IMAGE096
Figure DEST_PATH_IMAGE097
Figure DEST_PATH_IMAGE098
Figure DEST_PATH_IMAGE099
Figure DEST_PATH_IMAGE100
Figure DEST_PATH_IMAGE101
Figure DEST_PATH_IMAGE102
Figure DEST_PATH_IMAGE103
Figure DEST_PATH_IMAGE104
Figure DEST_PATH_IMAGE105
Figure DEST_PATH_IMAGE106
Figure DEST_PATH_IMAGE107
Figure DEST_PATH_IMAGE108
Figure DEST_PATH_IMAGE109
Figure DEST_PATH_IMAGE110
Figure DEST_PATH_IMAGE111
Figure DEST_PATH_IMAGE112
Figure DEST_PATH_IMAGE113
Figure DEST_PATH_IMAGE114
Figure DEST_PATH_IMAGE115
Figure DEST_PATH_IMAGE116
Figure DEST_PATH_IMAGE117
Figure DEST_PATH_IMAGE118
Figure DEST_PATH_IMAGE119
Figure DEST_PATH_IMAGE120
Figure DEST_PATH_IMAGE121
Figure DEST_PATH_IMAGE122
Figure DEST_PATH_IMAGE123
Figure DEST_PATH_IMAGE124
Figure DEST_PATH_IMAGE125
Figure DEST_PATH_IMAGE126
Figure DEST_PATH_IMAGE127
Figure DEST_PATH_IMAGE128
Figure DEST_PATH_IMAGE129
Figure DEST_PATH_IMAGE130
Figure DEST_PATH_IMAGE131
Figure DEST_PATH_IMAGE132
Figure DEST_PATH_IMAGE133
Figure DEST_PATH_IMAGE134
Figure DEST_PATH_IMAGE135
Figure DEST_PATH_IMAGE136
Figure DEST_PATH_IMAGE137
Figure DEST_PATH_IMAGE138
Figure DEST_PATH_IMAGE139
Figure DEST_PATH_IMAGE140
Figure DEST_PATH_IMAGE141
Figure DEST_PATH_IMAGE142
Figure DEST_PATH_IMAGE143
Figure DEST_PATH_IMAGE144
Figure DEST_PATH_IMAGE145
Figure DEST_PATH_IMAGE146
Figure DEST_PATH_IMAGE147
Figure DEST_PATH_IMAGE148
Figure DEST_PATH_IMAGE149
Figure DEST_PATH_IMAGE150
Figure DEST_PATH_IMAGE151
Figure DEST_PATH_IMAGE152
Figure DEST_PATH_IMAGE153
Figure DEST_PATH_IMAGE154
Figure DEST_PATH_IMAGE155
Figure DEST_PATH_IMAGE156
Figure DEST_PATH_IMAGE157
Figure DEST_PATH_IMAGE158
Figure DEST_PATH_IMAGE159
Figure DEST_PATH_IMAGE160
Figure DEST_PATH_IMAGE161
Figure DEST_PATH_IMAGE162
Figure DEST_PATH_IMAGE163
Figure DEST_PATH_IMAGE164
Figure DEST_PATH_IMAGE165
Figure DEST_PATH_IMAGE166
Figure DEST_PATH_IMAGE167
Figure DEST_PATH_IMAGE168
Figure DEST_PATH_IMAGE169
Figure DEST_PATH_IMAGE170
Figure DEST_PATH_IMAGE171
Figure DEST_PATH_IMAGE172
Figure DEST_PATH_IMAGE173
Figure DEST_PATH_IMAGE174
Figure DEST_PATH_IMAGE175
Figure DEST_PATH_IMAGE176
Figure DEST_PATH_IMAGE177
Figure DEST_PATH_IMAGE178
Figure DEST_PATH_IMAGE179
Figure DEST_PATH_IMAGE180
Figure DEST_PATH_IMAGE181
Figure DEST_PATH_IMAGE182
Figure DEST_PATH_IMAGE183
Figure DEST_PATH_IMAGE184
Figure DEST_PATH_IMAGE185
Figure DEST_PATH_IMAGE186
Figure DEST_PATH_IMAGE187
Figure DEST_PATH_IMAGE188
Figure DEST_PATH_IMAGE189
Figure DEST_PATH_IMAGE190
Figure DEST_PATH_IMAGE191
Figure DEST_PATH_IMAGE192
Figure DEST_PATH_IMAGE193
Figure DEST_PATH_IMAGE194
Figure DEST_PATH_IMAGE195
Figure DEST_PATH_IMAGE196
Figure DEST_PATH_IMAGE197
Figure DEST_PATH_IMAGE198
Figure DEST_PATH_IMAGE199
Figure DEST_PATH_IMAGE200
Figure DEST_PATH_IMAGE201
Figure DEST_PATH_IMAGE202
Figure DEST_PATH_IMAGE203
Figure DEST_PATH_IMAGE204
Figure DEST_PATH_IMAGE205
Figure DEST_PATH_IMAGE206
Figure DEST_PATH_IMAGE207
Figure DEST_PATH_IMAGE208
Figure DEST_PATH_IMAGE209
Figure DEST_PATH_IMAGE210
Figure DEST_PATH_IMAGE211
Figure DEST_PATH_IMAGE212
Figure DEST_PATH_IMAGE213
Figure DEST_PATH_IMAGE214
Figure DEST_PATH_IMAGE215
Figure DEST_PATH_IMAGE216
Figure DEST_PATH_IMAGE217
Figure DEST_PATH_IMAGE218
Figure DEST_PATH_IMAGE219
Figure DEST_PATH_IMAGE220
Figure DEST_PATH_IMAGE221
Figure DEST_PATH_IMAGE222
Figure DEST_PATH_IMAGE223
Figure DEST_PATH_IMAGE224
Figure DEST_PATH_IMAGE225
Figure DEST_PATH_IMAGE226
Figure DEST_PATH_IMAGE227
Figure DEST_PATH_IMAGE228
Figure DEST_PATH_IMAGE229
Figure DEST_PATH_IMAGE230
Figure DEST_PATH_IMAGE231
Figure DEST_PATH_IMAGE232
Figure DEST_PATH_IMAGE233
Figure DEST_PATH_IMAGE234
Figure DEST_PATH_IMAGE235
Figure DEST_PATH_IMAGE236
Figure DEST_PATH_IMAGE237
Figure DEST_PATH_IMAGE238
Figure DEST_PATH_IMAGE239
Figure DEST_PATH_IMAGE240
Figure DEST_PATH_IMAGE241
Figure DEST_PATH_IMAGE242
Figure DEST_PATH_IMAGE243
Figure DEST_PATH_IMAGE244
Figure DEST_PATH_IMAGE245
Figure DEST_PATH_IMAGE246
Figure DEST_PATH_IMAGE247
Figure DEST_PATH_IMAGE248
Figure DEST_PATH_IMAGE249
Figure DEST_PATH_IMAGE250
Figure DEST_PATH_IMAGE251
Figure DEST_PATH_IMAGE252
Figure DEST_PATH_IMAGE253
Figure DEST_PATH_IMAGE254
Figure DEST_PATH_IMAGE255
Figure DEST_PATH_IMAGE256
Figure DEST_PATH_IMAGE257
Figure DEST_PATH_IMAGE258
Figure DEST_PATH_IMAGE259
Figure DEST_PATH_IMAGE260
Figure DEST_PATH_IMAGE261
Figure DEST_PATH_IMAGE262
Figure DEST_PATH_IMAGE263
Figure DEST_PATH_IMAGE264
Figure DEST_PATH_IMAGE265
Figure DEST_PATH_IMAGE266
。
6.制剂，其包含权利要求1或2所述的螺二芴化合物和至少一种溶剂，其中，所述溶剂为不饱和烃溶剂、饱和烃溶剂、醚类溶剂或酯类溶剂。
7.有机发光器件，其包括阴极层、阳极层和有机功能层，所述有机功能层为空穴注入层、空穴传输层、发光层、电子传输层和电子注入层中至少一层，其中，所述有机功能层包含权利要求1或2所述的螺二芴化合物。
8.根据权利要求7所述的有机发光器件，其中，所述有机功能层为发光层，所述发光层还包含客体化合物，其中，
所述螺二芴化合物与所述客体化合物的体积比为1：99至99：1；客体材料为荧光材料或磷光材料。
9.根据权利要求7所述的有机发光器件，其中，所述发光层还包含权利要求1或2所述的螺二芴化合物作为第一主体，另一种有机化合物作为第二主体，所述第一主体与第二主体的体积比为8：2至2：8。
10.根据权利要求7所述的有机发光器件，其中，所述有机功能层为电子传输层，所述螺二芴化合物可以单独形成电子传输层，也可以和掺杂剂共同形成电子传输层；当电子传输层中含有所述掺杂剂时，所述螺二芴化合物与所述掺杂剂的体积比为2：8~8：2；其中，所述掺杂剂为n型掺杂剂。
11.显示或照明装置，其包括权利要求7所述的有机发光器件。
CN202110951753.0A 2021-08-19 2021-08-19 螺二芴化合物、制剂、有机发光器件及显示或照明装置 Active CN113402498B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110951753.0A CN113402498B (zh) 2021-08-19 2021-08-19 螺二芴化合物、制剂、有机发光器件及显示或照明装置

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110951753.0A CN113402498B (zh) 2021-08-19 2021-08-19 螺二芴化合物、制剂、有机发光器件及显示或照明装置

Publications (2)

Publication Number Publication Date
CN113402498A true CN113402498A (zh) 2021-09-17
CN113402498B CN113402498B (zh) 2022-03-11

Family

ID=77688718

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110951753.0A Active CN113402498B (zh) 2021-08-19 2021-08-19 螺二芴化合物、制剂、有机发光器件及显示或照明装置

Country Status (1)

Country Link
CN (1) CN113402498B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115124433A (zh) * 2022-07-12 2022-09-30 北京八亿时空液晶科技股份有限公司 一种螺二芴衍生物及其应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013100464A1 (ko) * 2011-12-29 2013-07-04 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
CN106883215A (zh) * 2017-01-24 2017-06-23 瑞声科技（南京）有限公司 三嗪化合物及发光器件
KR20170075645A (ko) * 2015-12-23 2017-07-03 솔브레인 주식회사 신규한 유기화합물 및 이를 포함하는 유기전계발광소자
CN108997342A (zh) * 2018-08-20 2018-12-14 上海大学 一种多氮杂螺二芴化合物及含有该化合物的有机光电器件
CN109251194A (zh) * 2018-09-11 2019-01-22 长春海谱润斯科技有限公司 一种含芴类结构的三嗪化合物及其有机发光器件
CN109575001A (zh) * 2017-09-29 2019-04-05 Cmdl有限公司 3-二苯并呋喃基三嗪衍生物有机化合物及包含其的有机电致发光器件
CN110229071A (zh) * 2019-06-06 2019-09-13 北京诚志永华显示科技有限公司 芴衍生物有机电致发光器件

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013100464A1 (ko) * 2011-12-29 2013-07-04 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
KR20170075645A (ko) * 2015-12-23 2017-07-03 솔브레인 주식회사 신규한 유기화합물 및 이를 포함하는 유기전계발광소자
CN106883215A (zh) * 2017-01-24 2017-06-23 瑞声科技（南京）有限公司 三嗪化合物及发光器件
CN109575001A (zh) * 2017-09-29 2019-04-05 Cmdl有限公司 3-二苯并呋喃基三嗪衍生物有机化合物及包含其的有机电致发光器件
CN108997342A (zh) * 2018-08-20 2018-12-14 上海大学 一种多氮杂螺二芴化合物及含有该化合物的有机光电器件
CN109251194A (zh) * 2018-09-11 2019-01-22 长春海谱润斯科技有限公司 一种含芴类结构的三嗪化合物及其有机发光器件
CN110229071A (zh) * 2019-06-06 2019-09-13 北京诚志永华显示科技有限公司 芴衍生物有机电致发光器件

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115124433A (zh) * 2022-07-12 2022-09-30 北京八亿时空液晶科技股份有限公司 一种螺二芴衍生物及其应用

Also Published As

Publication number Publication date
CN113402498B (zh) 2022-03-11

Similar Documents

Publication Publication Date Title
JP2019220710A (ja) 発光素子、発光モジュール、照明装置、及び電子機器
US9353085B2 (en) Compound for organic electroluminescent device and organic electroluminescent devices using the same
CN113248532B (zh) 一种有机化合物及含有该化合物的有机光电元件与应用
CN113501810B (zh) 一种有机化合物和含其的有机光电元件
CN112552282B (zh) 一种有机化合物和使用该化合物的有机光电元件
Zhao et al. Highly efficient green and red OLEDs based on a new exciplex system with simple structures
KR20130121597A (ko) 트리페닐아민을 사용한 정공 수송 물질 및 이를 포함한 유기 전계 발광 소자
CN112979478B (zh) 一种化合物及其应用、包含其的有机电致发光器件
KR20130121516A (ko) 신규한 아릴아민을 사용한 정공 수송 물질 및 이를 포함한 유기 전계 발광 소자
CN109638170B (zh) 一种有机电致光电元件
CN113402498B (zh) 螺二芴化合物、制剂、有机发光器件及显示或照明装置
KR101375542B1 (ko) 티오펜 유도체를 포함하는 정공수송 물질 및 이를 사용한 유기전계 발광소자
KR101311840B1 (ko) 신규한 3차 아릴 아민 및 이를 포함한 유기전계 발광소자
CN110872315A (zh) 一种有机化合物和使用该化合物的有机电致发光器件
KR102304989B1 (ko) 유기발광 화합물 및 이를 포함하는 유기발광소자
CN113013346B (zh) 三元组合物和含有该组合物的有机电致发光元件及应用
CN110627685A (zh) 一种空穴注入材料、包含其的空穴注入层和oled显示面板
KR20140079078A (ko) 인광 화합물 및 이를 이용한 유기발광다이오드소자
CN115894446A (zh) 一种氮杂螺二芴化合物及包含其的制剂、有机发光元件及显示或照明装置
KR102209237B1 (ko) 유기 전기 발광 소자용 발광 재료, 이를 이용한 유기 전기 발광 소자 및 유기 전기 발광 소자용 재료
CN113248522B (zh) 一种有机化合物及使用该化合物的有机发光器件
CN113416536B (zh) 一种主客体组合物及包含该组合物的有机电致发光元件
CN117186139A (zh) 一种硼氮化合物及其使用该化合物的有机电致器件
TW201323379A (zh) 用於有機電致發光裝置之發光之１，１’－雙萘基－４，４’－二胺衍生物及使用該衍生物之有機電致發光裝置
KR101329047B1 (ko) 아민계 정공수송 물질 및 이를 포함한 유기전계 발광소자

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant