WO2019062686A1 - 一种以氰基苯为核心的化合物及其在oled器件上的应用 - Google Patents

一种以氰基苯为核心的化合物及其在oled器件上的应用 Download PDF

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WO2019062686A1
WO2019062686A1 PCT/CN2018/107223 CN2018107223W WO2019062686A1 WO 2019062686 A1 WO2019062686 A1 WO 2019062686A1 CN 2018107223 W CN2018107223 W CN 2018107223W WO 2019062686 A1 WO2019062686 A1 WO 2019062686A1
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陈海峰
李崇
张兆超
张小庆
唐丹丹
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江苏三月光电科技有限公司
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    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to the field of semiconductor technology, and in particular to a compound containing cyanobenzene as a core and its application to an organic light emitting diode.
  • OLED Organic Light Emission Diodes
  • the OLED light-emitting device is like a sandwich structure, including an electrode material film layer and an organic functional material sandwiched between different electrode film layers, and various functional materials are superposed on each other according to the purpose to form an OLED light-emitting device.
  • Thermally activated delayed fluorescence (TADF) materials are the third generation of organic luminescent materials developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference ( ⁇ E ST ), and triplet excitons can be converted into singlet exciton luminescence by anti-system enthalpy. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation, and the internal quantum efficiency of the device can reach 100%.
  • the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the field of OLEDs is broad.
  • the Applicant has provided a compound containing cyanobenzene as a core and its use in an organic electroluminescent device.
  • the compound of the invention is based on the TADF mechanism with cyanobenzene as the core and as a light-emitting layer material for the organic light-emitting diode.
  • the device made by the invention has good photoelectric performance and can meet the requirements of the panel manufacturer.
  • the technical solution of the present invention is as follows:
  • the Applicant has provided a compound having cyanobenzene as a core, and the structure of the compound is as shown in the general formula (1):
  • X 1 and X 2 are each independently represented by a cyano group or a hydrogen atom; X 1 and X 2 are not the same; in the formula (1), R 1 and R 2 are each independently represented as a hydrogen atom. a substituted or unsubstituted C 6-60 aryl group, a substituted or unsubstituted 5-60 membered heteroaryl group containing one or more hetero atoms; the hetero atom is nitrogen, oxygen or sulfur; R 1 and R 2 At the same time, it is a hydrogen atom; in the formula (1), Ar is represented by a single bond, a substituted or unsubstituted C 6-60 arylene group, and a substituted or unsubstituted 5-60-membered impurity containing one or more hetero atoms. An arylene group; the hetero atom is nitrogen, oxygen or sulfur; in the formula (1), R represents a structure represented by the formula (2);
  • the structure of the compound is as shown in the formula (5) or the formula (6):
  • the structure of the compound is as shown in the formula (7), the formula (8), the formula (9) or the formula (10):
  • the structure of the compound is as shown in the formula (11), the formula (12), the formula (13) or the formula (14):
  • R 1 and R 2 are each independently represented by a hydrogen atom, a phenyl group, a biphenyl group, a naphthyl group or an anthracenyl group; and Ar is represented by a single bond, a phenylene group, a biphenylylene group, a naphthylene group or an anthracene group.
  • One of the bases are independently represented by a hydrogen atom, a phenyl group, a biphenyl group, a naphthyl group or an anthracenyl group; and Ar is represented by a single bond, a phenylene group, a biphenylylene group, a naphthylene group or an anthracene group.
  • R is expressed as:
  • the Applicant also provides a method of preparing the compound, the reaction equation occurring during the preparation is:
  • the specific preparation steps are as follows: the raw material brominated product E1 and the aminated product RH are dissolved in anhydrous toluene, and after deoxidation, Pd 2 (dba) 3 and tri-tert-butylphosphine are added, and the reaction is carried out at 95 to 110 ° C in an inert atmosphere at 10 to 24 During the reaction, the reaction progress was continuously monitored by TLC during the reaction. After the reaction of the raw materials was completed, the reaction was cooled, filtered, and the filtrate was evaporated to remove the solvent.
  • the crude product was passed through a silica gel column to obtain the target compound; the molar ratio of the bromo compound E1 to RH
  • the molar ratio of Pd 2 (dba) 3 to bromo E1 is from 0.006 to 0.02:1
  • the molar ratio of tri-tert-butylphosphine to bromo E1 is from 0.006 to 0.02:1
  • sodium tert-butoxide is from 1:1.0 to 1.5.
  • the molar ratio to the brominated E1 is 2.0 to 3.0:1;
  • the intermediate M2 and the raw material E2 are dissolved in a mixed solution of toluene and ethanol, and after deoxidation, Pd(PPh 3 ) 4 and K 2 CO 3 are added , and the reaction is carried out at 95 to 110 ° C for 10 to 24 hours in an inert atmosphere.
  • the reaction process is continuously monitored by TLC. After the reaction of the raw materials is completed, the reaction is cooled, filtered, and the filtrate is evaporated to remove the solvent.
  • the crude product is passed through a silica gel column to obtain the target compound; the amount of the toluene and ethanol is used per gram of the intermediate M2.
  • the molar ratio of the raw material E2 to the intermediate M2 is (1 to 1.5): 1
  • the molar ratio of Pd(PPh 3 ) 4 to the intermediate M2 is (0.006 to 0.02): 1
  • the molar ratio of K 2 CO 3 to the intermediate M2 was (1.5 to 2): 1.
  • the Applicant also provides a light emitting device comprising the compound, the light emitting device comprising the compound.
  • the Applicant also provides a light emitting device comprising the compound, the light emitting layer material of the light emitting device comprising the compound for use in fabricating an OLED device.
  • the Applicant also provides an illumination or display element comprising the organic electroluminescent device described above.
  • the compound of the invention has cyanobenzene as the mother core, the cyanophenyl group is in the same plane, has stronger rigidity, and thus has better film forming property; the cyanophenyl group is a strong electron withdrawing group, and
  • the carbazole ring group can form a strong charge transfer effect, and has a small energy level difference between the S1 state and the T1 state, thereby realizing the reverse intersystem enthalpy under thermal stimulation conditions, and the conditions at the energy level are met. At the same time, it has bipolar and TADF effects.
  • cyanobenzene due to the chemical stability and thermal stability of cyano group, cyanobenzene has good industrial application prospect and is suitable for use as the main material of the luminescent layer. Further, such compounds can also be used as doping materials for the light-emitting layer materials depending on the molecular design of the materials.
  • the compound of the present invention When the compound of the present invention is used as a light-emitting layer material of an OLED light-emitting device, the current efficiency, power efficiency and external quantum efficiency of the device are greatly improved; at the same time, the life of the device is greatly improved.
  • the compound material of the invention has good application effect in the OLED light-emitting device and has good industrialization prospect.
  • 1 is a schematic view showing the structure of a device to which the compound of the present invention is applied; wherein 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light-emitting layer, and 6 is an electron transport layer. 7 is an electron injection layer, and 8 is a cathode reflection electrode layer.
  • Figure 2 shows the current efficiency as a function of temperature.
  • R 3 is represented by a hydrogen atom and R 4 does not represent a hydrogen atom:
  • the raw material II and the intermediate S1 are weighed, dissolved in toluene, and a mixed solution of potassium carbonate, tetrakistriphenylphosphine palladium, ethanol and water is added under an inert atmosphere, and the mixture is heated to 110 to 120 ° C for 10 to 24 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, and the filtrate is separated.
  • intermediate S2 The organic phase is evaporated to dryness to dryness to dryness eluted to silica gel column to afford intermediate S2; in the above reaction, the molar ratio of intermediate S1 to starting material II is 1: 1 ⁇ 2; the molar ratio of intermediate S1 to potassium carbonate is 1:1 to 3; the molar ratio of intermediate S1 to tetrakistriphenylphosphine palladium is 1:0.01-0.05;
  • the intermediate S2 is dissolved in o-dichlorobenzene under an inert atmosphere, and then triphenylphosphine is added, and the reaction is stirred at 170 to 190 ° C for 12 to 16 hours. After the reaction is completed, it is cooled to room temperature, filtered, and the filtrate is depressurized. Evaporating to no fraction, passing through a silica gel column to obtain intermediate M1; in the above reaction, the molar ratio of intermediate S2 to triphenylphosphine is 1:1 to 2;
  • the intermediate M1 the raw material III, the sodium t-butoxide, the Pd 2 (dba) 3 and the tri-tert-butylphosphine were weighed in turn, stirred and mixed with toluene, heated to 110-120 ° C, and refluxed for 12-24. After the hour, the sample plate was sampled, showing that there was no intermediate M1 remaining, the reaction was complete; it was naturally cooled to room temperature, filtered, and the filtrate was subjected to vacuum distillation to a fraction without distillation, and passed through a neutral silica gel column to obtain intermediate M2.
  • the molar ratio of the intermediate M1 to the raw material III is 1:1 to 2; the molar ratio of the intermediate M1 to the sodium t-butoxide is 1:1 to 3; the molar ratio of the intermediate M1 to the Pd 2 (dba) 3 1:0.01 ⁇ 0.05; the molar ratio of intermediate M1 to tri-tert-butylphosphine is 1:0.01-0.05;
  • Elemental analysis structure C 6 H 4 BrNO 2 calcd for C3,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,
  • the raw material II and the intermediate S1 are weighed, dissolved in toluene, and a mixed solution of potassium carbonate, tetrakistriphenylphosphine palladium, ethanol and water is added under an inert atmosphere, and the mixture is heated to 110 to 120 ° C for 10 to 24 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, and the filtrate is separated.
  • intermediate S2 The organic phase is evaporated to dryness to dryness to dryness eluted to silica gel column to afford intermediate S2; in the above reaction, the molar ratio of intermediate S1 to starting material II is 1: 1 ⁇ 2; the molar ratio of intermediate S1 to potassium carbonate is 1:1 to 3; the molar ratio of intermediate S1 to tetrakistriphenylphosphine palladium is 1:0.01-0.05;
  • the intermediate S2 is dissolved in o-dichlorobenzene under an inert atmosphere, and then triphenylphosphine is added, and the reaction is stirred at 170 to 190 ° C for 12 to 16 hours. After the reaction is completed, it is cooled to room temperature, filtered, and the filtrate is depressurized. Evaporating to no fraction, passing through a silica gel column to obtain intermediate M1; in the above reaction, the molar ratio of intermediate S2 to triphenylphosphine is 1:1 to 2;
  • the intermediate M1 the raw material III, the sodium t-butoxide, the Pd 2 (dba) 3 and the tri-tert-butylphosphine were weighed in turn, stirred and mixed with toluene, heated to 110-120 ° C, and refluxed for 12-24. After the hour, the sample plate was sampled, showing that there was no intermediate M1 remaining, the reaction was complete; it was naturally cooled to room temperature, filtered, and the filtrate was subjected to vacuum distillation to a fraction without distillation, and passed through a neutral silica gel column to obtain intermediate M2.
  • the molar ratio of the intermediate M1 to the raw material III is 1:1 to 2; the molar ratio of the intermediate M1 to the sodium t-butoxide is 1:1 to 3; the molar ratio of the intermediate M1 to the Pd 2 (dba) 3 It is 1:0.01-0.05; the molar ratio of intermediate M1 to tri-tert-butylphosphine is 1:0.01-0.05; taking intermediate M2-2 as an example:
  • Elemental analysis structure C 24 H 13 NO 2 Theory C, 82.98; H, 3.77; N, 4.03; Tests: C, 82.97; H, 3.77; N, 4.02; ESI-MS (m/z) (M+ ): The theoretical value is 347.09, and the measured value is 347.51.
  • Intermediate M1 was prepared from the synthesis scheme of intermediate M1-6; intermediate M2 was prepared from the synthesis scheme of intermediate M2-2; the specific structure used in the preparation process is shown in Table 1:
  • the rate of analysis is 72.3%; Elemental analysis structure (Molecular formula C 37 H 22 N 2 S): Theory C, 84.38; H, 4.21; N, 5.32; S, 6.09; Test value: C, 84.38; H, 4.21; N, 5.33 ;S, 6.08; ESI-MS (m/z) (M+): 520.15.
  • the rate of the elemental analysis structure (Molecular Formula C 40 H 28 N 2 ): Theoretical value C, 89.52; H, 5.26; N, 5.22; Test value: C, 89.53; H, 5.27; N, 5.21.; m/z) (M+): The theoretical value is 536.23, found 536.61.
  • the rate of the elemental analysis structure (Molecular Formula C 43 H 27 N 3 ): Theoretical value C, 88.18; H, 4.65; N, 7.17; Test value: C, 88.10; H, 4.66; N, 7.15; ESI-MS ( m/z) (M+): The theoretical value is 585.22, found 585.75.
  • the compound of the present invention can be used as a light-emitting layer material, and the thermal performance, the luminescence spectrum and the cyclic volt-ampere stability of the compound 6, the compound 96, the compound 126 and the conventional material CBP of the present invention are tested. The test results are shown in Table 2.
  • the thermal weight loss temperature Td is the temperature at which the weight loss is 1% in a nitrogen atmosphere. It is measured on a TGA-50H thermogravimetric analyzer from Shimadzu Corporation, Japan. The nitrogen flow rate is 20 mL/min; ⁇ PL is the fluorescence emission wavelength of the sample solution.
  • test sample dissolved in a volume ratio of 2:1 A mixed solvent of methyl chloride and acetonitrile at a concentration of 1 mg/mL, and the electrolyte is an organic solution of 0.1 M tetrabutylammonium tetrafluoroborate or tetrabutylammonium hexafluorophosphate.
  • the reference electrode is an Ag/Ag+ electrode
  • the counter electrode is a titanium plate
  • the working electrode is an ITO electrode
  • the compound of the present invention has good redox stability, high thermal stability, and suitable luminescence spectrum, so that the efficiency and lifetime of the OLED device using the compound of the present invention as a light-emitting layer material are improved.
  • the application effects of the compound synthesized by the present invention as a host material of the light-emitting layer in the device will be described in detail below by Examples 22 to 31 and Comparative Examples 1, 2 and 3.
  • the structural composition of the device obtained in each example is shown in Table 3.
  • the test results of the obtained device are shown in Table 4.
  • the weight ratio is mixed, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al).
  • the structure of the materials involved is as follows:
  • the light emitting layer 5 of the OLED light emitting device is fabricated, and the structure thereof includes the material compound 16 used as the host material of the OLED light emitting layer 5, and GD19 is used as a doping material, and the doping ratio of the doping material is 5%.
  • the weight ratio of the light-emitting layer was 30 nm.
  • the vacuum evaporation of the electron transport layer material was continued to be TPBI.
  • the vacuum evaporation film thickness of this material was 40 nm, and this layer was the electron transport layer 6.
  • a lithium fluoride (LiF) layer having a film thickness of 1 nm was formed by a vacuum evaporation apparatus, and this layer was an electron injection layer 7.
  • an aluminum (Al) layer having a film thickness of 80 nm was formed by a vacuum deposition apparatus, and this layer was used as the cathode reflective electrode layer 8.
  • Example 22 10.6 11.1
  • Example 29 37.7 23.0
  • Example 23 11.6 12.1
  • Example 30 56.9 27.8
  • Example 24 10.1 14.7
  • Example 31 58.9 29.4
  • Example 25 36.0 19.8 Comparative example 1 6.5 3.8
  • Example 26 34.1 22.1 Comparative example 2 24.6 4.3
  • Example 27 31.1 18.8 Comparative example 3 25.1 7.8
  • Example 28 35.2 20.9
  • the current efficiency of Comparative Example 1 was 6.5 cd/A (@10 mA/cm 2 ); the lifetime decay of LT95 at 5000 nit brightness was 3.8 Hr.
  • the current efficiency of Comparative Example 2 was 24.6 cd/A (@10 mA/cm 2 ); the lifetime decay of LT95 at 5000 nit brightness was 4.3 Hr.
  • the current efficiency of Comparative Example 3 was 25.1 cd/A (@10 mA/cm 2 ); the lifetime decay of LT95 at 5000 nit brightness was 7.8 Hr.
  • the life test system is the OLED device life tester jointly researched by the owner of the invention and Shanghai University.
  • the compound of the present invention has good application effects as an luminescent layer material in an OLED light-emitting device, and has a good industrialization prospect. Further, the OLED device prepared by the material of the present invention is relatively stable when operating at a low temperature, and the device examples 22, 25, and 30 and the device comparative example 1, the comparative example 2, and the comparative example 3 are in the range of -10 to 80 °C. The test results are shown in Table 4 and Figure 2.
  • device embodiments 22, 25, and 30 are device structures in which the materials of the present invention and known materials are matched, and compared with the device comparative example 1, the comparative example 2, and the comparative example 3, not only the low temperature efficiency. High, and the efficiency rises steadily during the temperature rise.

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Abstract

本发明公开了一种以氰基苯为核心的化合物及其在OLED器件上的应用，该化合物以氰基苯为核心，以咔唑并环基团为支链。该化合物具有分子间不易结晶、不易聚集、具有良好成膜性的特点。将本发明化合物作为发光层材料应用于有机电致发光器件上，应用本发明化合物的有机电致发光器件具有良好的光电性能表现，可以更好的适应和满足面板制造企业的应用要求。

Description

一种以氰基苯为核心的化合物及其在OLED器件上的应用 技术领域
本发明涉及半导体技术领域，尤其是涉及一种含氰基苯为核心的化合物，以及其在有机发光二极管上的应用。
背景技术
有机电致发光(OLED:Organic Light Emission Diodes)器件技术既可以用来制造新型显示产品，也可以用于制作新型照明产品，有望替代现有的液晶显示和荧光灯照明，应用前景十分广泛。OLED发光器件犹如三明治的结构，包括电极材料膜层，以及夹在不同电极膜层之间的有机功能材料，各种不同功能材料根据用途相互叠加在一起共同组成OLED发光器件。作为电流器件，当对OLED发光器件的两端电极施加电压，并通过电场作用有机层功能材料膜层中的正负电荷，正负电荷进一步在发光层中复合，即产生OLED电致发光。
有机发光二极管(OLEDs)在大面积平板显示和照明方面的应用引起了工业界和学术界的广泛关注。然而，传统有机荧光材料只能利用电激发形成的25％单线态激子发光，器件的内量子效率较低(最高为25％)。外量子效率普遍低于5％，与磷光器件的效率还有很大差距。尽管磷光材料由于重原子中心强的自旋-轨道耦合增强了系间窜越，可以有效利用电激发形成的单线态激子和三线态激子发光，使器件的内量子效率达100％。但磷光材料存在价格昂贵，材料稳定性较差，器件效率滚落严重等问题限制了其在OLEDs的应用。热激活延迟荧光(TADF)材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有小的单线态-三线态能级差(△E ST)，三线态激子可以通过反系间窜越转变成单线态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子，器件的内量子效率可以达到100％。同时，材料结构可控，性质稳定，价格便宜无需贵重金属，在OLEDs领域的应用前景广阔。
虽然理论上TADF材料可以实现100％的激子利用率，但实际上存在如下问题:(1)设计分子的T1和S1态具有强的CT特征，非常小的S1-T1态能隙，虽然可以通过TADF过程实现高T 1→S 1态激子转化率，但同时导致低的S1态辐射跃迁速率，因此，难于兼具(或同时实现)高激子利用率和高荧光辐射效率；(2)即使已经采用掺杂器件减轻T激子浓度猝灭效应，大多数TADF材料的器件在高电流密度下效率滚降严重。就当前OLED显示照明产业的实际需求而言，目前OLED材料的发展还远远不够，落后于面板制造企业的要求，作为材料企业开发更高性能的有机功能材料显得尤为重要。
发明内容
针对现有技术存在的上述问题，本申请人提供了一种以含氰基苯为核心的化合物及其在有机电致发光器件上的应用。本发明化合物基于TADF机理以含氰基苯为核心，作为发光层材料应用于有机发光二极管，本发明制作的器件具有良好的光电性能，能够满足面板制造企业的要求。本发明的技术方案如下：
本申请人提供了一种以氰基苯为核心的化合物，所述化合物的结构如通式(1)所示：
Figure PCTCN2018107223-appb-000001
通式(1)中，X 1、X 2分别独立的表示为氰基或氢原子；X 1与X 2不相同；通式(1)中，R 1、R 2分别独立的表示为氢原子、取代或未取代的C 6-60芳基、含有一个或多个杂原子的取代或未取代的5-60元杂芳基；所述杂原子为氮、氧或硫；R 1与R 2不同时为氢原子；通式(1)中，Ar表示为单键、取代或未取代的C 6-60亚芳基、含有一个或多个杂原子的取代或未取代的5～60元杂亚芳基；所述杂原子为氮、氧或硫；通式(1)中，R表示为通式(2)所示结构；
Figure PCTCN2018107223-appb-000002
通式(2)中，R 3、R 4分别独立的表示为氢原子、通式(3)或通式(4)中结构；R 3、R 4可以相同或不同；
Figure PCTCN2018107223-appb-000003
通式(3)和通式(4)中，X 3、X 4、X 5分别独立的表示为氧原子、硫原子、C 1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基取代的亚胺基或芳基取代的亚胺基中的一种；通式(3)、通式(4)通过C L1-C L2键、C L2-C L3键、C L3-C L4键、C L’1-C L’2键、C L'2-C L’3键或C L’3-C L’4键和通式(2)并环连接。
优选的，所述化合物的结构如通式(5)或通式(6)所示：
Figure PCTCN2018107223-appb-000004
其中使用的符号和标记如上所述。
优选的，所述化合物的结构如通式(7)、通式(8)、通式(9)或通式(10)所示：
Figure PCTCN2018107223-appb-000005
其中使用的符号和标记如上所述。
优选的，所述化合物的结构如通式(11)、通式(12)、通式(13)或通式(14)所示：
Figure PCTCN2018107223-appb-000006
其中使用的符号和标记如上所述。
优选的，R 1、R 2分别独立的表示为氢原子、苯基、联苯基、萘基或蒽基；Ar表示为单键、亚苯基、亚联苯基、亚萘基或亚蒽基的一种。
更优选的，所述R表示为：
Figure PCTCN2018107223-appb-000007
Figure PCTCN2018107223-appb-000008
Figure PCTCN2018107223-appb-000009
中的任意一种。更优选的，所述化合物的具体结构式为：
Figure PCTCN2018107223-appb-000010
Figure PCTCN2018107223-appb-000011
Figure PCTCN2018107223-appb-000012
Figure PCTCN2018107223-appb-000013
Figure PCTCN2018107223-appb-000014
Figure PCTCN2018107223-appb-000015
Figure PCTCN2018107223-appb-000016
中的任意一种。
本申请人还提供了一种制备所述化合物的方法，制备过程中发生的反应方程式是：
当Ar表示单键时：
Figure PCTCN2018107223-appb-000017
具体制备步骤为：将原料溴代物E1与胺化物R-H溶解于无水甲苯中，除氧后加入Pd 2(dba) 3和三叔丁基磷,在惰性气氛下95～110℃反应10～24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到目标化合物；所述溴代物E1与R-H的摩尔比为1:1.0～1.5，Pd 2(dba) 3与溴代物E1的摩尔比为0.006～0.02:1，三叔丁基膦与溴代物E1的摩尔比为0.006～0.02:1，叔丁醇钠与溴代物E1的摩尔比为2.0～3.0:1；
当Ar不表示单键时：
Figure PCTCN2018107223-appb-000018
将中间体M2和原料E2溶解于甲苯和乙醇的混合溶液中，除氧后加入Pd(PPh 3) 4和K 2CO 3，在惰性气氛下95～110℃反应10～24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到目标化合物；所述的甲苯和乙醇的用量为每克中间体M2使用30～50mL甲苯和5～10mL乙醇，原料E2与中间体M2的摩尔比为(1～1.5):1，Pd(PPh 3) 4与中间体M2的摩尔比为(0.006～0.02):1，K 2CO 3与中间体M2的摩尔比为(1.5～2):1。
本申请人还提供了一种包含所述化合物的发光器件，所述发光器件包括所述化合物。本申请人还提供了一种包含所述化合物的发光器件，所述发光器件的发光层材料包括所述化合物，用于制作OLED器件。本申请人还提供了一种照明或显示元件，包括上面所述的有机电致发光器件。本发明有益的技术效果在于：
本发明化合物以氰基苯为母核，氰基苯基团处在同一个平面，具有更强的刚性，因此具有更好的成膜性；氰基苯基团是强吸电子基团，与咔唑并环类基团可形成较强的电荷转移作用，且具有较小的S1态和T1态的能级差，从而在热刺激条件下实现反向系间窜越，在能级符合的 条件下同时具有双极性和TADF效应；同时由于氰基的化学稳定性和热稳定性，氰基苯具有较好的工业应用前景，适合作为发光层主体材料使用。进一步的，根据材料分子设计的不同，此类化合物也可以作为发光层材料的掺杂材料使用。
本发明化合物作为OLED发光器件的发光层材料使用时，器件的电流效率，功率效率和外量子效率均得到很大改善；同时，对于器件寿命提升非常明显。本发明所述化合物材料在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。
附图说明
图1为本发明化合物应用的器件结构示意图；其中，1为透明基板层，2为ITO阳极层，3为空穴注入层，4为空穴传输层，5为发光层，6为电子传输层，7为电子注入层，8为阴极反射电极层。图2为电流效率随温度的变化曲线。
具体实施方式
首先提供中间体通式(1)中
Figure PCTCN2018107223-appb-000019
的合成路线为：
R 3表示为氢原子、R 4不表示氢原子时：
Figure PCTCN2018107223-appb-000020
称取原料I溶于乙酸中，用冰盐浴降温至0℃；称取液溴溶于冰醋酸中，缓慢滴加至含有硝基化合物原料I的乙酸溶液中，室温搅拌反应6～12小时，反应结束后，滴加氢氧化钠水溶液中和反应液，用二氯甲烷萃取，取有机相过滤，滤液减压旋蒸至无馏分，过硅胶柱，得中间体S1；上述反应中，原料I与液溴的摩尔比例为1:1～3；
称取原料Ⅱ和中间体S1，用甲苯溶解，在惰性气氛下，加入碳酸钾、四三苯基膦钯、乙醇和水的混合溶液，搅拌升温至110～120℃，反应10～24小时，反应结束后，冷却至室温，过滤，滤液分层，取有机相减压旋蒸至无馏分，过硅胶柱，得到中间体S2；上述反应中，中间体S1与原料Ⅱ的摩尔比为1:1～2；中间体S1与碳酸钾的摩尔比为1:1～3；中间体S1与四三苯基膦钯的摩尔比为1:0.01～0.05；
在惰性气氛下，将中间体S2溶于邻二氯苯中，再加入三苯基膦，在170～190℃下搅拌反应 12～16小时，反应结束后冷却至室温，过滤，滤液减压旋蒸至无馏分，过硅胶柱，得到中间体M1；上述反应中，中间体S2与三苯基膦摩尔比为1:1～2；
在氮气保护下，依次称取中间体M1、原料Ⅲ、叔丁醇钠、Pd 2(dba) 3、三叔丁基膦，用甲苯搅拌混合，加热至110～120℃，回流反应12～24小时，取样点板，显示无中间体M1剩余，反应完全；自然冷却至室温，过滤，滤液进行减压旋蒸至无馏分，过中性硅胶柱，得到中间体M2。上述反应中，中间体M1与原料Ⅲ摩尔比为1:1～2；中间体M1与叔丁醇钠的摩尔比为1:1～3；中间体M1与Pd 2(dba) 3的摩尔比为1:0.01～0.05；中间体M1与三叔丁基膦的摩尔比为1:0.01～0.05；
以中间体M2-1为例：
Figure PCTCN2018107223-appb-000021
在250ml的三口瓶中，加入0.04mol的硝基苯、100ml乙酸，搅拌溶解，用冰盐浴降温至0℃；称取0.05mol Br 2溶于50ml乙酸，将溴的乙酸溶液缓慢滴加至上述反应体系中，滴加结束后，升至室温，搅拌反应12小时；取样点板，显示无硝基苯剩余，反应完全；加NaOH水溶液中和反应液，用二氯甲烷萃取，分层，取有机相过滤，滤液减压旋蒸至无馏分，过中性硅胶柱，得到中间体S1-1，HPLC纯度99.4％，收率78.9％；
元素分析结构C 6H 4BrNO 2：理论值C,35.68；H,2.00；Br,39.56；N,6.93；测试值：C,35.68；H,2.00；Br,39.56；N,6.92；ESI-MS(m/z)(M+)：理论值为200.94，实测值为201.51。
在250ml的三口瓶中，通氮气保护下，加入0.05mol中间体S1-1、0.06mol原料II-1、100ml甲苯，搅拌混合，再加入0.0025mol Pd(PPh 3) 4、0.075mol碳酸钾、50ml水和乙醇1:1的混合液，搅拌升温至120℃，回流反应24小时，取样点板，显示无中间体S1-1剩余，反应完全；自然冷却至室温，过滤，滤液分层，取有机相减压旋蒸至无馏分，过中性硅胶柱，得到中间体S2-1，HPLC纯度99.6％，收率69.2％；
元素分析结构C 18H 11NO 3：理论值C,74.73；H,3.83；N,4.84；测试值：C,74.73；H,3.83；N,4.83；ESI-MS(m/z)(M+)：理论值为289.07，实测值为289.59。
在250ml的三口瓶中，通氮气保护下，加入0.04mol中间体S2-1、0.05mol三苯基膦、100ml邻二氯苯，搅拌混合，加热至180℃，反应12小时，取样点板，显示无中间体S2-1剩余，反应完全；自然冷却至室温，过滤，滤液减压旋蒸至无馏分，过中性硅胶柱，得到中间体M1-6， HPLC纯度99.7％，收率71.5％；元素分析结构C 18H 11NO：理论值C,84.03；H,4.31；N,5.44；测试值：C,84.03；H,4.31；N,5.45；ESI-MS(m/z)(M+)：理论值为257.08，实测值为257.04。
在250ml的三口瓶中，通氮气保护下，加入0.03mol中间体M1-6、0.036mol 1,4-二溴苯、150ml甲苯，搅拌混合，再加入0.09mol叔丁醇钠、0.002molPd 2(dba) 3、0.002mol三叔丁基膦，搅拌加热至115℃，回流反应24小时，取样点板，显示无中间体M1-6剩余，反应完全；自然冷却至室温，过滤，滤液减压旋蒸至无馏分，过中性硅胶柱，得到中间体M2-1，HPLC纯度99.0％，收率68.0％；元素分析结构C 24H 14BrNO：理论值C,69.92；H,3.42；Br,19.38；N,3.40；测试值：C,69.92；H,3.42；Br,19.38；N,3.41；ESI-MS(m/z)(M+)：理论值为411.03，实测值为411.69。
R 3、R 4均不表示氢原子时：
Figure PCTCN2018107223-appb-000022
称取原料I溶于乙酸中，用冰盐浴降温至0℃；称取液溴溶于冰醋酸中，缓慢滴加至含有硝基化合物原料I的乙酸溶液中，室温搅拌反应6～12小时，反应结束后，滴加氢氧化钠水溶液中和反应液，用二氯甲烷萃取，取有机相过滤，滤液减压旋蒸至无馏分，过硅胶柱，得中间体S1；上述反应中，原料I与液溴的摩尔比例为1:1～3；
称取原料Ⅱ和中间体S1，用甲苯溶解，在惰性气氛下，加入碳酸钾、四三苯基膦钯、乙醇和水的混合溶液，搅拌升温至110～120℃，反应10～24小时，反应结束后，冷却至室温，过滤，滤液分层，取有机相减压旋蒸至无馏分，过硅胶柱，得到中间体S2；上述反应中，中间体S1与原料Ⅱ的摩尔比为1:1～2；中间体S1与碳酸钾的摩尔比为1:1～3；中间体S1与四三苯基膦钯的摩尔比为1:0.01～0.05；
在惰性气氛下，将中间体S2溶于邻二氯苯中，再加入三苯基膦，在170～190℃下搅拌反应12～16小时，反应结束后冷却至室温，过滤，滤液减压旋蒸至无馏分，过硅胶柱，得到中间体M1；上述反应中，中间体S2与三苯基膦摩尔比为1:1～2；
在氮气保护下，依次称取中间体M1、原料Ⅲ、叔丁醇钠、Pd 2(dba) 3、三叔丁基膦，用甲苯搅拌混合，加热至110～120℃，回流反应12～24小时，取样点板，显示无中间体M1剩余，反应完全；自然冷却至室温，过滤，滤液进行减压旋蒸至无馏分，过中性硅胶柱，得到中间体M2。上述反应中，中间体M1与原料Ⅲ摩尔比为1:1～2；中间体M1与叔丁醇钠的摩尔比为1:1～3；中间体M1与Pd 2(dba) 3的摩尔比为1:0.01～0.05；中间体M1与三叔丁基膦的摩尔比为 1:0.01～0.05；以中间体M2-2为例：
Figure PCTCN2018107223-appb-000023
在250ml的三口瓶中，加入0.04mol的3-硝基二苯并[b，d]呋喃、100ml乙酸，搅拌溶解，用冰盐浴降温至0℃；称取0.05mol Br 2溶于50ml乙酸，将溴的乙酸溶液缓慢滴加至上述反应体系中，滴加结束后，升至室温，搅拌反应12小时；取样点板，显示无3-硝基二苯并[b，d]呋喃剩余，反应完全；加NaOH水溶液中和反应液，用二氯甲烷萃取，分层，取有机相过滤，滤液减压旋蒸至无馏分，过中性硅胶柱，得到中间体S1-2，HPLC纯度99.3％，收率68.9％；元素分析结构C 12H 6BrNO 3：理论值C,49.35；H,2.07；Br,27.36；N,4.80；测试值：C,49.33；H,2.08；Br,27.37；N,4.81；ESI-MS(m/z)(M+)：理论值为290.95，实测值为291.90。
在250ml的三口瓶中，通氮气保护下，加入0.05mol中间体S1-2、0.06mol原料II-2、100ml甲苯，搅拌混合，再加入0.0025mol Pd(PPh 3) 4、0.075mol碳酸钾、50ml水和乙醇1:1的混合液，搅拌升温至120℃，回流反应24小时，取样点板，显示无中间体S1-2剩余，反应完全；自然冷却至室温，过滤，滤液分层，取有机相减压旋蒸至无馏分，过中性硅胶柱，得到中间体S2-2，HPLC纯度99.0％，收率78.2％；元素分析结构C 24H 13NO 4：理论值C,75.98；H,3.45；N,3.69；测试值：C,75.96；H,3.45；N,3.68；ESI-MS(m/z)(M+)：理论值为379.08，实测值为379.80。
在250ml的三口瓶中，通氮气保护下，加入0.04mol中间体S2-2、0.05mol三苯基膦、100ml邻二氯苯，搅拌混合，加热至180℃，反应12小时，取样点板，显示无中间体S2-2剩余，反应完全；自然冷却至室温，过滤，滤液减压旋蒸至无馏分，过中性硅胶柱，得到中间体M1-7，HPLC纯度99.2％，收率75.5％；元素分析结构C 24H 13NO 2：理论值C,82.98；H,3.77；N,4.03；测试值：C,82.97；H,3.77；N,4.02；ESI-MS(m/z)(M+)：理论值为347.09，实测值为347.51。
在250ml的三口瓶中，通氮气保护下，加入0.03mol中间体M1-7、0.036mol 1,4-二溴苯、150ml甲苯，搅拌混合，再加入0.09mol叔丁醇钠、0.002molPd 2(dba) 3、0.002mol三叔丁基膦，搅拌加热至115℃，回流反应24小时，取样点板，显示无中间体M1-7剩余，反应完全；自然冷却至室温，过滤，滤液减压旋蒸至无馏分，过中性硅胶柱，得到中间体M2-2，HPLC纯度99.8％，收率75.1％；元素分析结构C 30H 16BrNO 2：理论值C,71.73；H,3.21；Br,15.91；N,2.79；测试值：C,71.72；H,3.21；Br,15.90；N,2.80；ESI-MS(m/z)(M+)：理论值为501.04，实测值为501.98。
由中间体M1-6的合成方案制备中间体M1；由中间体M2-2的合成方案制备中间体M2；制备过程中所采用的的具体结构如表1所示：
表1
Figure PCTCN2018107223-appb-000024
Figure PCTCN2018107223-appb-000025
Figure PCTCN2018107223-appb-000026
实施例1：化合物6的合成：
Figure PCTCN2018107223-appb-000027
将0.01mol原料E1-1与0.012mol中间体M1-1溶解于150mL无水甲苯中，除氧后加入0.0005mol Pd 2(dba) 3和0.015mol三叔丁基磷,在惰性气氛下110℃反应24个小时,反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率76.7％；元素分析结构(分子式C 37H 22N 2O)：理论值C,87.04；H,4.34；N,5.49；测试值：C,87.02；H,4.33；N,5.50；ESI-MS(m/z)(M+)：理论值为510.17，实测值为509.98。
实施例2：化合物16的合成：
Figure PCTCN2018107223-appb-000028
将0.01mol原料E1-2与0.012mol中间体M1-2溶解于150mL无水甲苯中，除氧后加入0.0005mol Pd 2(dba) 3和0.015mol三叔丁基磷,在惰性气氛下110℃反应24个小时,反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅 胶柱，得到中间体目标产物，HPLC纯度99.9％，收率72.3％；元素分析结构(分子式C 37H 22N 2S)：理论值C,84.38；H,4.21；N,5.32；S,6.09；测试值：C,84.38；H,4.21；N,5.33；S,6.08；ESI-MS(m/z)(M+)：理论值为526.15，实测值为526.01。
实施例3：化合物26的合成：
Figure PCTCN2018107223-appb-000029
将0.01mol原料E1-1与0.012mol中间体M1-3溶解于150mL无水甲苯中，除氧后加入0.0005mol Pd 2(dba) 3和0.015mol三叔丁基磷,在惰性气氛下110℃反应24个小时,反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率81.2％；元素分析结构(分子式C 40H 28N 2)：理论值C,89.52；H,5.26；N,5.22；测试值：C,89.50；H,5.26；N,5.21；ESI-MS(m/z)(M+)：理论值为536.23，实测值为536.60。
实施例4：化合物36的合成：
Figure PCTCN2018107223-appb-000030
将0.01mol原料E1-2与0.012mol中间体M1-4溶解于150mL无水甲苯中，除氧后加入0.0005mol Pd 2(dba) 3和0.015mol三叔丁基磷,在惰性气氛下110℃反应24个小时,反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率84.6％；元素分析结构(分子式C 40H 28N 2)：理论值C,89.52；H,5.26；N,5.22；测试值：C,89.53；H,5.27；N,5.21；ESI-MS(m/z)(M+)：理论值为536.23，实测值为536.61。
实施例5：化合物46的合成：
Figure PCTCN2018107223-appb-000031
将0.01mol原料E1-1与0.012mol中间体M1-5溶解于150mL无水甲苯中，除氧后加入0.0005mol Pd 2(dba) 3和0.015mol三叔丁基磷,在惰性气氛下110℃反应24个小时,反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅 胶柱，得到中间体目标产物，HPLC纯度99.9％，收率82.9％；元素分析结构(分子式C 43H 27N 3)：理论值C,88.18；H,4.65；N,7.17；测试值：C,88.10；H,4.66；N,7.15；ESI-MS(m/z)(M+)：理论值为585.22，实测值为585.75。
实施例6：化合物56的合成：
Figure PCTCN2018107223-appb-000032
将0.01mol中间体M2-1和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率79.2％；元素分析结构(分子式C 43H 26N 2O)：理论值C,88.03；H,4.47；N,4.77；测试值：C,88.00；H,4.47；N,4.76；ESI-MS(m/z)(M+)：理论值为586.20，实测值为586.60。
实施例7：化合物66的合成：
Figure PCTCN2018107223-appb-000033
将0.01mol中间体M2-2和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率78.2％；元素分析结构(分子式C 49H 28N 2O 2)：理论值C,86.96；H,4.17；N,4.14；测试值：C,86.97；H,4.18；N,4.13；ESI-MS(m/z)(M+)：理论值为676.22，实测值为676.80。
实施例8：化合物76的合成：
Figure PCTCN2018107223-appb-000034
将0.01mol中间体M2-3和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率88.8％； 元素分析结构(分子式C 43H 26N 2S)：理论值C,85.69；H,4.35；N,4.65；S,5.32；测试值：C,85.67；H,4.35；N,4.66；S,5.33；ESI-MS(m/z)(M+)：理论值为602.18，实测值为602.62。
实施例9：化合物86的合成：
Figure PCTCN2018107223-appb-000035
将0.01mol中间体M2-4和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率79.3％；元素分析结构(分子式C 46H 32N 2)：理论值C,90.16；H,5.26；N,4.57；测试值：C,90.17；H,5.27；N,4.56；ESI-MS(m/z)(M+)：理论值为612.26，实测值为612.42。
实施例10：化合物96的合成：
Figure PCTCN2018107223-appb-000036
将0.01mol中间体M2-5和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率79.3％；元素分析结构(分子式C 46H 32N 2)：理论值C,90.16；H,5.26；N,4.57；测试值：C,90.17；H,5.27；N,4.56；ESI-MS(m/z)(M+)：理论值为612.26，实测值为612.42。
实施例11：化合物106的合成：
Figure PCTCN2018107223-appb-000037
将0.01mol中间体M2-6和0.012mol原料E2-2溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率74.2％；元素分析结构(分子式C 46H 32N 2)：理论值C,90.16；H,5.26；N,4.57；测试值：C,90.18；H,5.25； N,4.56；ESI-MS(m/z)(M+)：理论值为612.26，实测值为612.38。
实施例12：化合物116的合成：
Figure PCTCN2018107223-appb-000038
将0.01mol中间体M2-7和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率81.2％；元素分析结构(分子式C 55H 40N 2)：理论值C,90.63；H,5.53；N,3.84；测试值：C,90.62；H,5.54；N,3.84；ESI-MS(m/z)(M+)：理论值为728.32，实测值为728.90。
实施例13：化合物126的合成：
Figure PCTCN2018107223-appb-000039
将0.01mol中间体M2-8和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率82.6％；元素分析结构(分子式C 49H 31N 3)：理论值C,88.93；H,4.72；N,6.35；测试值：C,88.91；H,4.73；N,6.36；ESI-MS(m/z)(M+)：理论值为661.25，实测值为661.90。
实施例14：化合物136的合成：
Figure PCTCN2018107223-appb-000040
将0.01mol中间体M2-9和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率84.9％；元素分析结构(分子式C 49H 30N 2O)：理论值C,88.80；H,4.56；N,4.23；测试值：C,88.79；H,4.57；N,4.24；ESI-MS(m/z)(M+)：理论值为662.24，实测值为662.86。
实施例15：化合物146的合成：
Figure PCTCN2018107223-appb-000041
将0.01mol中间体M2-10和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率81.3％；元素分析结构(分子式C 49H 30N 2S)：理论值C,86.70；H,4.45；N,4.13；S,4.72；测试值：C,86.72；H,4.45；N,4.12；S,4.71；ESI-MS(m/z)(M+)：理论值为678.21，实测值为678.89。
实施例16：化合物156的合成：
Figure PCTCN2018107223-appb-000042
将0.01mol中间体M2-11和0.012mol原料E2-2溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率78.7％；元素分析结构(分子式C 52H 36N 2)：理论值C,90.67；H,5.27；N,4.07；测试值：C,90.67；H,5.27；N,4.06；ESI-MS(m/z)(M+)：理论值为688.29，实测值为689.10。
实施例17：化合物166的合成：
Figure PCTCN2018107223-appb-000043
将0.01mol中间体M2-12和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率77.0％；元素分析结构(分子式C 52H 36N 2)：理论值C,90.67；H,5.27；N,4.07；测试值：C,90.66；H,5.26；N,4.08；ESI-MS(m/z)(M+)：理论值为688.29，实测值为688.50。
实施例18：化合物176的合成：
Figure PCTCN2018107223-appb-000044
将0.01mol中间体M2-13和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率78.0％；元素分析结构(分子式C 55H 35N 3)：理论值C,89.52；H,4.78；N,5.69；测试值：C,89.53；H,4.77；N,5.70；ESI-MS(m/z)(M+)：理论值为737.28，实测值为737.95。
实施例19：化合物186的合成：
Figure PCTCN2018107223-appb-000045
将0.01mol中间体M2-14和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率82.6％；元素分析结构(分子式C 43H 26N 2O 2)：理论值C,85.69；H,4.35；N,4.65；测试值：C,85.70；H,4.36；N,4.64；ESI-MS(m/z)(M+)：理论值为602.20，实测值为602.80。
实施例20：化合物196的合成：
Figure PCTCN2018107223-appb-000046
将0.01mol中间体M2-15和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率78.0％；元素分析结构(分子式C 61H 52N 2)：理论值C,90.11；H,6.45；N,3.45；测试值：C,90.11；H,6.45； N,3.44；ESI-MS(m/z)(M+)：理论值为812.41，实测值为813.00。
实施例21：化合物206的合成：
Figure PCTCN2018107223-appb-000047
将0.01mol中间体M2-16和0.012mol原料E2-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体目标产物，HPLC纯度99.9％，收率78.0％；元素分析结构(分子式C 58H 41N 3)：理论值C,89.31；H,5.30；N,5.39；测试值：C,89.31；H,5.31；N,5.38；ESI-MS(m/z)(M+)：理论值为779.33，实测值为780.22。
本发明化合物可以作为发光层材料使用，对本发明化合物6、化合物96、化合物126、现有材料CBP进行热性能、发光光谱及循环伏安稳定性的测试，测试结果如表2所示。
表2
化合物 Td(℃) λ PL(nm) 循环伏安稳定性
化合物6 425 469 优
化合物96 439 462 优
化合物126 449 475 优
材料CBP 353 369 差
注：热失重温度Td是在氮气气氛中失重1％的温度，在日本岛津公司的TGA-50H热重分析仪上进行测定，氮气流量为20mL/min；λ PL是样品溶液荧光发射波长，利用日本拓普康SR-3分光辐射度计测定；循环伏安稳定性是通过循环伏安法观测材料的氧化还原特性来进行鉴定；测试条件：测试样品溶于体积比为2:1的二氯甲烷和乙腈混合溶剂，浓度1mg/mL，电解液是0.1M的四氟硼酸四丁基铵或六氟磷酸四丁基铵的有机溶液。参比电极是Ag/Ag+电极，对电极为钛板，工作电极为ITO电极，循环次数为20次。
由上表数据可知，本发明化合物具有较好的氧化还原稳定性，较高的热稳定性，合适的发光光谱，使得应用本发明化合物作为发光层材料的OLED器件效率和寿命得到提升。以下通过实施例22～31和比较例1、2、3详细说明本发明合成的化合物在器件中作为发光层主体材料的应用效果。各实施例所得器件的结构组成如表3所示。所得器件的测试结果见表4所示。
实施例22
透明基板层1/ITO阳极层2/空穴注入层3(三氧化钼MoO 3，厚度10nm)/空穴传输层4(TAPC， 厚度80nm)/发光层5(化合物16和GD19按照100：5的重量比混掺，厚度30nm)/电子传输层6(TPBI，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al)。涉及到的材料结构式如下：
Figure PCTCN2018107223-appb-000048
具体制备过程如下：
透明基板层1为透明基材，如透明PI膜、玻璃等。对ITO阳极层2(膜厚为150nm)进行洗涤，即依次进行碱洗涤、纯水洗涤、干燥，再进行紫外线-臭氧洗涤以清除透明ITO表面的有机残留物。在进行了上述洗涤之后的ITO阳极层2上，利用真空蒸镀装置，蒸镀膜厚为10nm的三氧化钼MoO 3作为空穴注入层3使用。紧接着蒸镀80nm厚度的TAPC作为空穴传输层4。上述空穴传输材料蒸镀结束后，制作OLED发光器件的发光层5，其结构包括OLED发光层5所使用材料化合物16作为主体材料，GD19作为掺杂材料，掺杂材料掺杂比例为5％重量比，发光层膜厚为30nm。在上述发光层5之后，继续真空蒸镀电子传输层材料为TPBI。该材料的真空蒸镀膜厚为40nm，此层为电子传输层6。在电子传输层6上，通过真空蒸镀装置，制作膜厚为1nm的氟化锂(LiF)层，此层为电子注入层7。在电子注入层7上，通过真空蒸镀装置，制作膜厚为80nm的铝(Al)层，此层为阴极反射电极层8使用。如上所述地完成OLED发光器件后，用公知的驱动电路将阳极和阴极连接起来，测量器件的电流效率以及器件的寿命。
表3
Figure PCTCN2018107223-appb-000049
Figure PCTCN2018107223-appb-000050
表4
器件代号 电流效率 LT95寿命 器件代号 电流效率 LT95寿命
实施例22 10.6 11.1 实施例29 37.7 23.0
实施例23 11.6 12.1 实施例30 56.9 27.8
实施例24 10.1 14.7 实施例31 58.9 29.4
实施例25 36.0 19.8 比较例1 6.5 3.8
实施例26 34.1 22.1 比较例2 24.6 4.3
实施例27 31.1 18.8 比较例3 25.1 7.8
实施例28 35.2 20.9      
说明:比较例1的电流效率为6.5cd/A(@10mA/cm 2)；5000nit亮度下LT95寿命衰减为3.8Hr。比较例2的电流效率为24.6cd/A(@10mA/cm 2)；5000nit亮度下LT95寿命衰减为4.3Hr。比较例3的电流效率为25.1cd/A(@10mA/cm 2)；5000nit亮度下LT95寿命衰减为7.8Hr。寿命测试系统为本发明所有权人与上海大学共同研究的OLED器件寿命测试仪。
由表3的结果可以看出本发明所述化合物可应用于OLED发光器件制作，并且与比较例1、2、3相比，无论是效率还是寿命均获得较大改观，特别是器件的驱动寿命获得较大的提升。
从实施例所提供的测试数据来看，本发明化合物作为发光层材料在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。进一步的本发明材料制备的OLED器件在低温下工作时效率也比较稳定，将器件实施例22、25、30和器件比较例1、比较例2、比较例3在-10～80℃区间进行效率测试，所得结果如表4和图2所示。
表5
Figure PCTCN2018107223-appb-000051
从表4和图2的数据可知，器件实施例22、25、30为本发明材料和已知材料搭配的器件结构，和器件比较例1、比较例2、比较例3相比，不仅低温效率高，而且在温度升高过程中，效率平稳升高。
虽然已通过实施例和优选实施方式公开了本发明，但应理解，本发明不限于所公开的实施方式。相反，本领域技术人员应明白，其意在涵盖各种变型和类似的安排。因此，所附权利要求的范围应与最宽的解释相一致以涵盖所有这样的变型和类似的安排。

Claims (11)

  1. 一种以氰基苯为核心的化合物，其特征在于所述化合物的结构如通式(1)所示：
    Figure PCTCN2018107223-appb-100001
    通式(1)中，X 1、X 2分别独立的表示为氰基或氢原子；X 1与X 2不相同；
    通式(1)中，R 1、R 2分别独立的表示为氢原子、取代或未取代的C 6-60芳基、含有一个或多个杂原子的取代或未取代的5-60元杂芳基；所述杂原子为氮、氧或硫；R 1与R 2不同时为氢原子；
    通式(1)中，Ar表示为单键、取代或未取代的C 6-60亚芳基、含有一个或多个杂原子的取代或未取代的5～60元杂亚芳基；所述杂原子为氮、氧或硫；
    通式(1)中，R表示为通式(2)所示结构；
    Figure PCTCN2018107223-appb-100002
    通式(2)中，R 3、R 4分别独立的表示为氢原子、通式(3)或通式(4)中结构；R 3、R 4可以相同或不同；
    Figure PCTCN2018107223-appb-100003
    通式(3)和通式(4)中，X 3、X 4、X 5分别独立的表示为氧原子、硫原子、C 1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基取代的亚胺基或芳基取代的亚胺基中的一种；
    通式(3)、通式(4)通过C L1-C L2键、C L2-C L3键、C L3-C L4键、C L’1-C L’2键、C L'2-C L’3键或C L’3-C L’4键和通式(2)并环连接。
  2. 根据权利要求1所述的化合物，其特征在于，所述化合物的结构如通式(5)或通式(6)所示：
    Figure PCTCN2018107223-appb-100004
    其中使用的符号和标记具有权利要求1中给出的含义。
  3. 根据权利要求1所述的化合物，其特征在于，所述化合物的结构如通式(7)、通式(8)、通式(9)或通式(10)所示：
    Figure PCTCN2018107223-appb-100005
    其中使用的符号和标记具有权利要求1中给出的含义。
  4. 根据权利要求1所述的化合物，其特征在于，所述化合物的结构如通式(11)、通式(12)、通式(13)或通式(14)所示：
    Figure PCTCN2018107223-appb-100006
    其中使用的符号和标记具有权利要求1中给出的含义。
  5. 根据权利要求1所述的有机化合物，其特征在于R 1、R 2分别独立的表示为氢原子、苯 基、联苯基、萘基或蒽基；Ar表示为单键、亚苯基、亚联苯基、亚萘基或亚蒽基的一种。
  6. 根据权利要求1所述的有机化合物，其特征在于所述R表示为：
    Figure PCTCN2018107223-appb-100007
    Figure PCTCN2018107223-appb-100008
    Figure PCTCN2018107223-appb-100009
    Figure PCTCN2018107223-appb-100010
    中的任意一种。
  7. 根据权利要求1所述的化合物，其特征在于所述化合物的具体结构式为：
    Figure PCTCN2018107223-appb-100011
    Figure PCTCN2018107223-appb-100012
    Figure PCTCN2018107223-appb-100013
    Figure PCTCN2018107223-appb-100014
    Figure PCTCN2018107223-appb-100015
    Figure PCTCN2018107223-appb-100016
    Figure PCTCN2018107223-appb-100017
    Figure PCTCN2018107223-appb-100018
    Figure PCTCN2018107223-appb-100019
    中的任意一种。
  8. 一种制备权利要求1～7任一项所述化合物的方法，其特征在于制备过程中发生的反应方程式是：
    当Ar表示单键时：
    Figure PCTCN2018107223-appb-100020
    具体制备步骤为：
    将原料溴代物E1与胺化物R-H溶解于无水甲苯中，除氧后加入Pd 2(dba) 3和三叔丁基磷,在惰性气氛下95～110℃反应10～24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到目标化合物；所述溴代物E1与R-H的摩尔比为1:1.0～1.5，Pd 2(dba) 3与溴代物E1的摩尔比为0.006～0.02:1，三叔丁基膦与溴代物E1的摩尔比为0.006～0.02:1，叔丁醇钠与溴代物E1的摩尔比为2.0～3.0:1；
    当Ar不表示单键时
    Figure PCTCN2018107223-appb-100021
    将中间体M2和原料E2溶解于甲苯和乙醇的混合溶液中，除氧后加入Pd(PPh 3) 4和K 2CO 3，在惰性气氛下95～110℃反应10～24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到目标化合物；所述的甲苯和乙醇的用量为每克中间体M2使用30～50mL甲苯和5～10mL乙醇，原料E2与中间体M2的摩尔比为(1～1.5):1，Pd(PPh 3) 4与中间体M2的摩尔比为(0.006～0.02):1，K 2CO 3与中间体M2的摩尔比为(1.5～2):1。
  9. 一种有机电致发光器件，其特征在于，所述有机电致发光器件包括至少一层功能层含有权利要求1～7任一项所述的以氰基苯为核心的有机化合物。
  10. 一种有机电致发光器件，包括发光层，其特征在于，所述发光层含有权利要求1～7任一项所述的以氰基苯为核心的有机化合物。
  11. 一种照明或显示元件，其特征在于，包括如权利要求9所述的有机电致发光器件。
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