WO2018019254A1 - 一种基于二芳基酮的化合物及其应用 - Google Patents

一种基于二芳基酮的化合物及其应用 Download PDF

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WO2018019254A1
WO2018019254A1 PCT/CN2017/094481 CN2017094481W WO2018019254A1 WO 2018019254 A1 WO2018019254 A1 WO 2018019254A1 CN 2017094481 W CN2017094481 W CN 2017094481W WO 2018019254 A1 WO2018019254 A1 WO 2018019254A1
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based compound
ketone
compound
compound according
light
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PCT/CN2017/094481
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French (fr)
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王立春
张兆超
李崇
徐凯
叶中华
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江苏三月光电科技有限公司
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Definitions

  • the present invention relates to the field of semiconductor technology, and in particular to a compound containing a diaryl ketone and its use as an luminescent layer material on an organic light emitting diode.
  • OLED Organic Light Emission Diodes
  • 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.
  • T1 and S1 states of the design molecule have strong CT characteristics, and very small S1-T1 state energy gaps, although High T 1 ⁇ S 1 state exciton conversion is achieved by the TADF process, but at the same time results in a low S1 state radiation transition rate, and therefore, it is difficult to achieve (or simultaneously achieve) high exciton utilization and high fluorescence radiation efficiency; Even though doped devices have been used to mitigate the T exciton concentration quenching effect, most TADF material devices have a significant efficiency roll-off at high current densities.
  • the Applicant has provided a diaryl ketone-based compound and its use in an organic electroluminescent device.
  • the compound of the invention is applied to the OLED as a host material and a doping material of the light-emitting layer based on the TADF mechanism, and the OLED device produced has good photoelectric performance and can meet the requirements of the panel manufacturer.
  • the Applicant has provided a diaryl ketone-based compound whose structure is as shown in the general formula (1):
  • n 1 or 2;
  • Ar is represented by phenyl, naphthyl or biphenyl
  • R 1 and R 2 are each independently selected from a hydrogen atom, a phenyl group or a structure represented by the formula (2):
  • X 1 and X 2 are each independently represented by an oxygen atom, a sulfur atom, a selenium atom, a C 1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl group or an aryl group.
  • R 1 and R 2 are not simultaneously a hydrogen atom.
  • R 1 and R 2 are simultaneously taken as a phenyl group, Expressed as:
  • the specific structural formula of the compound is:
  • the Applicant also provides a process for preparing the diaryl ketone-based compound, the reaction equation in which the preparation is:
  • the bromoaryl ketone and The molar ratio is 1:1.2-3.0, the molar ratio of Pd 2 (dba) 3 to bromoaryl ketone is 0.006-0.02:1, and the molar ratio of tri-tert-butylphosphine to bromoaryl ketone is 0.006-0.02.
  • the molar ratio of sodium tert-butoxide to bromoaryl ketone is from 2.0 to 5.0:1.
  • the applicant also provides a light-emitting device containing the above-described diaryl ketone-based compound, characterized in that the compound is used as a light-emitting layer host material for an organic light-emitting diode.
  • the Applicant also provides a light-emitting device comprising the above-described diaryl ketone-based compound, characterized in that the compound is used as a light-emitting layer doping material for an organic light-emitting diode.
  • the compound of the invention has a diaryl ketone as a mother nucleus, and two aromatic heterocyclic groups are attached to both sides, thereby avoiding the aggregation between molecules, and the molecules are mostly rigid groups, and have good film forming property and fluorescence quantum efficiency. It can be used as a light-emitting layer doping material; the combination of an electron donor (donor, D) and an electron acceptor (acceptor, A) in the compound structure molecule can increase orbital overlap and improve luminous efficiency, and connect two sides on both sides.
  • the compound of the invention has a wide energy band, a wide range of HOMO energy levels, and a D-group triplet energy level (T1) which is high enough to be matched with a carbazole material to form a doped double host material with complementary properties.
  • T1 D-group triplet energy level
  • the doping of the double body makes the holes and electrons of the material system more balanced, and the wide range of HOMO and LUMO levels is more favorable for hole and electron injection.
  • the doped double-substance luminescent material has a significant effect on the luminescence and lifetime characteristics of OLED luminescent devices. At present, this technology has been widely used in mass production.
  • the compound of the invention can be used as a light-emitting layer material for OLED light-emitting device fabrication, and can be used as a light-emitting layer host material or a doping material, respectively, to obtain good device performance, and current efficiency, power efficiency and external quantum efficiency of the device are obtained. Great improvement; at the same time, The increase in device life is very obvious.
  • the compound of the invention has good application effects in OLED light-emitting devices and has good industrialization prospects.
  • 1 is a schematic view showing the structure of a compound of the present invention applied to an OLED device
  • 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
  • 6 is an electron transport layer
  • 7 is an electron injection layer
  • 8 is a cathode reflective electrode.
  • Elemental analysis structure (Molecular formula C 53 H 32 N 2 O): Theory C, 89.30; H, 4.52; N, 3.93; O, 2.24; Test: C, 89.31; H, 4.51; N, 3.92; O, 2.26 .
  • HPLC-MS The molecular weight of the material was 712.83, and the measured molecular weight was 713.05.
  • Elemental analysis structure (Molecular Formula C 37 H 24 N 2 O): Theory C, 86.69; H, 4.72; N, 5.46; O, 3.12; Test: C, 86.69; H, 4.73; N, 5.47; O, 3.11 .
  • HPLC-MS The material had a molecular weight of 512.60 and a molecular weight of 512.85.
  • Elemental analysis structure (Molecular formula C 49 H 28 N 2 O 3 ): Theory C, 84.95; H, 4.07; N, 4.04; O, 6.93; Tests: C, 84.94; H, 4.08; N, 4.03; 6.95.
  • HPLC-MS The material had a molecular weight of 692.76 and a molecular weight of 692.97.
  • Elemental Analysis Structure (Molecular Formula C 55 H 40 N 2 O): Theory C, 88.68; H, 5.41; N, 3.76; O, 2.15; Tests: C, 88.71; H, 5.40; N, 3.75; O, 2.14 .
  • HPLC-MS The molecular weight of the material was 744.92, and the measured molecular weight was 745.23.
  • Elemental analysis structure (Molecular formula C 61 H 38 N 4 O): Theory C, 86.91; H, 4.54; N, 6.65; O, 1.90; Test: C, 86.91; H, 4.55; N, 6.65; O, 1.89 .
  • HPLC-MS The material had a molecular weight of 842.98 and a molecular weight of 843.35.
  • Elemental analysis structure (Molecular formula C 46 H 32 N 2 O): Theory C, 87.87; H, 5.13; N, 4.46; O, 2.54; Tests: C, 87.83; H, 5.15; N, 4.47; O, 2.55 .
  • HPLC-MS The material had a molecular weight of 628.76 and a molecular weight of 628.93.
  • Elemental Analysis Structure (Molecular Formula C 43 H 33 NO): Theory C, 89.09; H, 5.74; N, 2.42; O, 2.76; Tests: C, 89.07; H, 5.75; N, 2.43; O, 2.75.
  • HPLC-MS The material had a molecular weight of 579.73 and a molecular weight of 579.91.
  • Elemental analysis structure (Molecular formula C 37 H 21 NO 3 ): Theory C, 84.23; H, 4.01; N, 2.65; O, 9.10; Tests: C, 84.2; H, 4.02; N, 2.67; O, 9.11.
  • HPLC-MS The material had a molecular weight of 527.57 and a molecular weight of 527.74.
  • Elemental Analysis Structure (Molecular Formula C 43 H 33 NO): Theory C, 89.09; H, 5.74; N, 2.42; O, 2.76; ⁇ / RTI> C, 89.07; H, 5.75; N, 2.41; O, 2.77.
  • HPLC-MS The material had a molecular weight of 579.73 and a molecular weight of 579.91.
  • Elemental analysis structure (Molecular formula C 43 H 33 NO): Theory C, 89.09; H, 5.74; N, 2.42; O, 2.76; Tests: C, 89.1; H, 5.73; N, 2.40; O, 2.77.
  • HPLC-MS The material had a molecular weight of 579.73 and a molecular weight of 579.92.
  • Elemental Analysis Structure (Molecular Formula C 34 H 25 NO 2 ): Theory C, 85.15; H, 5.25; N, 2.92; O, 6.67; Test: C, 85.17; H, 5.24; N, 2.93; O, 6.66.
  • HPLC-MS The material had a molecular weight of 479.57 and a molecular weight of 479.74.
  • Elemental analysis structure (Molecular formula C 40 H 30 N 2 O): Theory C, 86.61; H, 5.45; N, 5.05; O, 2.88; Test: C, 86.65; H, 5.44; N, 5.05; O, 2.86 .
  • HPLC-MS The material had a molecular weight of 554.68 and a molecular weight of 554.87.
  • Elemental Analysis Structure (Molecular Formula C 34 H 25 NO 2 ): Theory C, 85.15; H, 5.25; N, 2.92; O, 6.67; Tests: C, 85.18; H, 5.25; N, 2.92; O, 6.65.
  • HPLC-MS The material had a molecular weight of 479.57 and a molecular weight of 479.81.
  • Elemental analysis structure (Molecular formula C 61 H 52 N 2 O): Theory C, 88.37; H, 6.32; N, 3.38; O, 1.93; Tests: C, 88.38; H, 6.31; N, 3.40; O, 1.91 .
  • HPLC-MS The material had a molecular weight of 829.08 and a molecular weight of 829.27.
  • Elemental analysis structure (Molecular formula C 41 H 30 N 2 O 3 ): Theory C, 82.25; H, 5.05; N, 4.68; O, 8.02; Tests: C, 82.26; H, 5.04; N, 4.67; 8.03.
  • HPLC-MS The material had a molecular weight of 598.69 and a molecular weight of 598.92.
  • Elemental analysis structure (Molecular formula C 43 H 33 NO 2 Se): Theory C, 76.55; H, 4.93; N, 2.08; O, 4.74; Se, 11.70; Tests: C, 76.54; H, 4.92; N, 2.09 ;O, 4.73; Se, 11.72.
  • HPLC-MS The material had a molecular weight of 674.69 and a molecular weight of 674.95.
  • Elemental analysis structure (Molecular formula C 49 H 31 N 3 O 3 ): Theory C, 82.92; H, 4.40; N, 5.92; O, 6.76; Tests: C, 82.92; H, 4.39; N, 5.91; 6.78.
  • HPLC-MS The molecular weight of the material was 709.79, and the measured molecular weight was 709.93.
  • Elemental analysis structure (Molecular formula C 39 H 26 N 2 O): Theory C, 86.96; H, 4.87; N, 5.20; O, 2.97; Tests: C, 86.99; H, 4.86; N, 5.19; O, 2.96 .
  • HPLC-MS The material had a molecular weight of 538.64 and a molecular weight of 538.82.
  • the physicochemical properties of the compounds of the present invention were characterized, wherein the compounds 3, 17, 63, 96, 136, 149 and the existing material CBP were measured for thermal properties, luminescence spectra and HOMO levels, and the test results are shown in Table 1.
  • 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. Measured by the Japanese Topcon SR-3 spectroradiometer; ⁇ f is the solid powder fluorescence quantum efficiency (using the US Ocean Optics Maya2000Pro fiber spectrometer, the US Lanfei C-701 integrating sphere and the ocean optical LLS-LED source) The solid fluorescence quantum efficiency test system was tested and determined by the method of Adv. Mater. 1997, 9, 230-232; the highest occupied molecular orbital HOMO level was tested by the photoelectron emission spectrometer (AC-2 type PESA) atmospheric environment test. .
  • AC-2 type PESA photoelectron emission spectrometer
  • the compound of the present invention has suitable HOMO, LUMO energy level and high thermal stability, and is suitable as a host material of the light-emitting layer; meanwhile, the compound of the present invention has a suitable luminescence spectrum and a high ⁇ f, so that The efficiency and lifetime of an OLED device using the compound of the present invention as a dopant material is improved.
  • Examples 22 to 30 and Comparative Examples 1 to 3 of the present invention have the same fabrication process as the device of the embodiment 22, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also uniform and different. It is a transformation of the host material and the doping material of the light-emitting layer 5 in the device.
  • the structural composition of the device obtained in each example is shown in Table 2.
  • the test results of the obtained device are shown in Table 3.
  • the weight ratio is mixed, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / Al.
  • the molecular structure of the relevant material is as follows:
  • the transparent substrate layer 1 is a transparent substrate such as a transparent PI film, glass, or the like.
  • the ITO anode layer 2 (having a film thickness of 150 nm) was washed, that is, washed with alkali, washed with pure water, dried, and subjected to ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO.
  • molybdenum trioxide MoO 3 having a thickness of 10 nm was deposited as a hole injecting layer 3 by a vacuum vapor deposition apparatus.
  • a TASC having a thickness of 80 nm was evaporated as the hole transport layer 4.
  • the light emitting layer 5 of the OLED light emitting device is fabricated, and the structure thereof includes the material compound 1 used as the host material of the OLED light emitting layer 5, and GD19 is used as the dopant 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.
  • the anode and the cathode are connected by a known driving circuit, and the current efficiency, the luminescence spectrum, and the lifetime of the device are measured.
  • the device examples and comparisons prepared in the same manner are shown in Table 2; the test results of the obtained devices are shown in Table 3.
  • the device preparation method of Table 2 and the test results of Table 3 show that Examples 22 to 24 are used as the light-emitting layer TADF host material for the OLED light-emitting device fabrication; and Examples 26 to 27 are the compounds of the present invention.
  • the luminescent layer host material is matched with the TADF doping material for the OLED light-emitting device fabrication; the embodiments 28-30 are used as the luminescent layer Co-host material and the carbazole host material for the OLED light-emitting device, and compared with the luminescent device. Compared with the examples 1, 2, and 3; both the efficiency and the lifetime are greatly improved compared with the known OLED materials.
  • the efficiency attenuation coefficient which represents the ratio between the difference between the maximum efficiency ⁇ 100 of the device and the maximum efficiency ⁇ m of the device at a driving current of 100 mA/cm 2 and the maximum efficiency. The larger the value, the more severe the device's efficiency roll-off, and conversely, the problem that the device decays rapidly at high current densities is controlled.
  • the compound of the present invention can be used as a light-emitting layer material, and the efficiency attenuation coefficient of the compound of the present invention 76, 81, 125 and the existing material CBP preparation device respectively The measurement results are shown in Table 6.

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Abstract

本发明公开了一种基于二芳基酮的化合物及其在有机电致发光器件上的应用，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，而且分子中的刚性基团可以提高材料的热稳定性。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

一种基于二芳基酮的化合物及其应用 技术领域
本发明涉及半导体技术领域，尤其是涉及一种含有二芳基酮的化合物，以及其作为发光层材料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)器件技术可以用来制造新型显示产品和照明产品，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。
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(△EST)，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T1→S1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基于二芳基酮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，作为发光层主体材料和掺杂材料应用于OLED，制作出的OLED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基于二芳基酮的化合物，所述化合物的结构如通式(1)所示：
Figure PCTCN2017094481-appb-000001
其中，
n＝1或2；
Ar表示为苯基、萘基或联苯基；
R1、R2分别独立的选取氢原子、苯基或通式(2)所示结构：
Figure PCTCN2017094481-appb-000002
其中，a为
Figure PCTCN2017094481-appb-000003
X1、X2分别独立的表示为氧原子、硫原子、硒原子、C1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基或芳基取代的叔胺基中的一种；a与CL1-CL2键、CL2-CL3键、CL3-CL4键、CL‘1-CL’2键、CL‘2-CL’3键或CL‘3-CL’4键连接。
优选的，R1、R2不同时为氢原子。
优选的，当R1、R2同时取苯基时，
Figure PCTCN2017094481-appb-000004
表示为：
Figure PCTCN2017094481-appb-000005
优选的，当通式(2)的a取
Figure PCTCN2017094481-appb-000006
时，
Figure PCTCN2017094481-appb-000007
表示为：
Figure PCTCN2017094481-appb-000008
Figure PCTCN2017094481-appb-000009
Figure PCTCN2017094481-appb-000010
Figure PCTCN2017094481-appb-000011
优选的，当通式(2)的a取
Figure PCTCN2017094481-appb-000012
时，
Figure PCTCN2017094481-appb-000013
表示为：
Figure PCTCN2017094481-appb-000014
优选的，当通式(2)的a取
Figure PCTCN2017094481-appb-000015
时，
Figure PCTCN2017094481-appb-000016
表示为：
Figure PCTCN2017094481-appb-000017
Figure PCTCN2017094481-appb-000018
Figure PCTCN2017094481-appb-000019
Figure PCTCN2017094481-appb-000020
Figure PCTCN2017094481-appb-000021
Figure PCTCN2017094481-appb-000022
Figure PCTCN2017094481-appb-000023
优选的，当通式(2)的a取
Figure PCTCN2017094481-appb-000024
时，
Figure PCTCN2017094481-appb-000025
表示为：
Figure PCTCN2017094481-appb-000026
Figure PCTCN2017094481-appb-000027
优选的，所述化合物的具体结构式为：
Figure PCTCN2017094481-appb-000028
Figure PCTCN2017094481-appb-000029
Figure PCTCN2017094481-appb-000030
Figure PCTCN2017094481-appb-000031
Figure PCTCN2017094481-appb-000032
Figure PCTCN2017094481-appb-000033
Figure PCTCN2017094481-appb-000034
中的任一种。
本申请人还提供了一种制备所述基于二芳基酮的化合物的方法，制备过程中的反应方程式是：
n＝1时，
Figure PCTCN2017094481-appb-000035
n＝2时，
Figure PCTCN2017094481-appb-000036
具体制备过程为：
称取溴代芳基酮和
Figure PCTCN2017094481-appb-000037
用甲苯溶解；再加入Pd2(dba)3、三叔丁基膦、叔丁醇钠；在惰性气氛下，将上述反应物的混合溶液于反应温度95～110℃，反应10～24小时，冷却并过滤反应溶液，滤液旋蒸，过硅胶柱，得到目标产物；
所述溴代芳基酮与
Figure PCTCN2017094481-appb-000038
的摩尔比为1:1.2～3.0，Pd2(dba)3与溴代芳基酮的摩尔比为0.006～0.02:1，三叔丁基膦与溴代芳基酮的摩尔比为0.006～0.02:1，叔丁醇钠与溴代芳基酮的摩尔比为2.0～5.0:1。
本申请人还提供了一种含有所述基于二芳基酮的化合物的发光器件，其特征在于所述化合物作为发光层主体材料，应用于有机发光二极管。
本申请人还提供了一种含有所述基于二芳基酮的化合物的发光器件，其特征在于所述化合物作为发光层掺杂材料，应用于有机发光二极管。
本发明有益的技术效果在于：
本发明化合物以二芳基酮为母核，两侧连接两个芳香杂环基团，避免了分子间的聚集作用，分子中多为刚性基团，具有好的成膜性和荧光量子效率，可以作为发光层掺杂材料使用；所述化合物结构分子内包含电子给体(donor，D)与电子受体(acceptor，A)的组合可以增加轨道重叠、提高发光效率，同时两侧连接两个芳香杂环基团以获得HOMO、LUMO空间分离的电荷转移态材料，实现小的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，适合作为发光层主体材料使用。
本发明化合物具有较宽的能带，HOMO能级范围较宽，并且所包含的D基团三线态能级(T1)足够高，可搭配咔唑类材料，形成性能互补的掺杂双主体材料，掺杂双主体搭配使材料体系的空穴、电子更均衡，宽范围的HOMO及LUMO能级更利于空穴及电子注入。掺杂双主体发光材料对于OLED发光器件的发光和寿命特性提升具有显著效果，目前，此技术已得到广泛的量产应用。
本发明所述化合物可作为发光层材料应用于OLED发光器件制作，并且分别作为发光层主体材料或掺杂材料，均可以获得良好的器件表现，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于OLED器件的结构示意图；
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。
具体实施方式
下面结合附图和实施例，对本发明进行具体描述。
实施例1：化合物3的合成
合成路线：
Figure PCTCN2017094481-appb-000039
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 4,4'-二溴二苯甲酮，0.025mol中间体A，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流24小时，取样点板，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度98.9％，收率65％。
元素分析结构(分子式C53H32N2O)：理论值C,89.30；H,4.52；N,3.93；O,2.24；测试值：C,89.31；H,4.51；N,3.92；O,2.26。HPLC-MS：材料分子量为712.83，实测分子量713.05。
实施例2：化合物10的合成
合成路线：
Figure PCTCN2017094481-appb-000040
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 4-溴二苯甲酮，0.015mol中间体B，0.02mol叔丁醇钠，5×10-5mol Pd2(dba)3，5×10-5mol三叔丁基膦，150ml甲苯，加热回流24小时，取样点板，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度99.4％，收率80％。
元素分析结构(分子式C37H24N2O)：理论值C,86.69；H,4.72；N,5.46；O,3.12；测试值：C,86.69；H,4.73； N,5.47；O,3.11。HPLC-MS：材料分子量为512.60，实测分子量512.85。
实施例3：化合物15的合成
合成路线：
Figure PCTCN2017094481-appb-000041
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 4,4'-二溴二苯甲酮，0.025mol中间体C，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流24小时，取样点板，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度99.1％，收率65％。
元素分析结构(分子式C49H28N2O3)：理论值C,84.95；H,4.07；N,4.04；O,6.93；测试值：C,84.94；H,4.08；N,4.03；O,6.95。
HPLC-MS：材料分子量为692.76，实测分子量692.97。
实施例4：化合物17的合成
合成路线：
Figure PCTCN2017094481-appb-000042
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 4,4'-二溴二苯甲酮，0.025mol中间体D，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流24小时，取样点板，反应完全。自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度98.8％，收率68％。
元素分析结构(分子式C55H40N2O)：理论值C,88.68；H,5.41；N,3.76；O,2.15；测试值：C,88.71；H,5.40；N,3.75；O,2.14。
HPLC-MS：材料分子量为744.92，实测分子量745.23。
实施例5：化合物18的合成
合成路线：
Figure PCTCN2017094481-appb-000043
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3,3'-二溴二苯甲酮，0.025mol中间体E，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流24小时，取样点板，反应完全。自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度99.1％，收率69％。
元素分析结构(分子式C61H38N4O)：理论值C,86.91；H,4.54；N,6.65；O,1.90；测试值：C,86.91；H,4.55；N,6.65；O,1.89。
HPLC-MS：材料分子量为842.98，实测分子量843.35。
实施例6：化合物24的合成
合成路线：
Figure PCTCN2017094481-appb-000044
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 4,4'-二溴二苯甲酮，0.025mol中间体F，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流24小时，取样点板，反应完全。自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度99.5％，收率72％。
元素分析结构(分子式C55H40N2O)：理论值C,88.68；H,5.41；N,3.76；O,2.15；测试值：C,88.71；H,5.42；N,3.73；O,2.14。HPLC-MS：材料分子量为744.92，实测分子量745.25。
实施例7：化合物39的合成
合成路线：
Figure PCTCN2017094481-appb-000045
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3-溴二苯甲酮，0.015mol中间体G，0.02mol叔丁醇钠，5×10-5mol Pd2(dba)3，5×10-5mol三叔丁基膦，150ml甲苯，加热回流24小时，取样点板，反应完全。自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度99.6％，收率66.％。
元素分析结构(分子式C46H32N2O)：理论值C,87.87；H,5.13；N,4.46；O,2.54；测试值：C,87.83；H,5.15；N,4.47；O,2.55。HPLC-MS：材料分子量为628.76，实测分子量628.93。
实施例8：化合物41的合成
体合成路线：
Figure PCTCN2017094481-appb-000046
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 4-溴二苯甲酮，0.015mol中间体H，0.02mol叔丁醇钠，5×10-5mol Pd2(dba)3，5×10-5mol三叔丁基膦，150ml甲苯，加热回流24小时，取样点板，反应完全。自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度99.5％，收率73％。
元素分析结构(分子式C43H33NO)：理论值C,89.09；H,5.74；N,2.42；O,2.76；测试值：C,89.07；H,5.75；N,2.43；O,2.75。HPLC-MS：材料分子量为579.73，实测分子量579.91。
实施例9：化合物50的合成
合成路线：
Figure PCTCN2017094481-appb-000047
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol联苯基-4-基-(4’-溴-联苯基-4-基)-甲酮，0.015mol中间体I，0.02mol叔丁醇钠，5×10-5mol Pd2(dba)3，5×10-5mol三叔丁基膦，150ml甲苯，加热回流24小时，取样点板，反应完全。自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度98.7％，收率64％。
元素分析结构(分子式C55H41NO)：理论值C,90.25；H,5.65；N,1.91；O,2.19；测试值：C,90.24；H,5.66；N,1.92；O,2.18。HPLC-MS：材料分子量为731.92，实测分子量732.21。
实施例10：化合物61的合成
合成路线：
Figure PCTCN2017094481-appb-000048
化合物61的制备方法同实施例2，不同之处在于用中间体J替换中间体B。
元素分析结构(分子式C37H21NO3)：理论值C,84.23；H,4.01；N,2.65；O,9.10；测试值：C,84.2；H,4.02；N,2.67；O,9.11。
HPLC-MS：材料分子量为527.57，实测分子量527.74。
实施例11：化合物63的合成
合成路线：
Figure PCTCN2017094481-appb-000049
化合物63的制备方法同实施例2，不同之处在于用中间体K替换中间体B。
元素分析结构(分子式C43H33NO)：理论值C,89.09；H,5.74；N,2.42；O,2.76；测试值：C,89.07；H,5.75；N,2.41；O,2.77。
HPLC-MS：材料分子量为579.73，实测分子量579.91。
实施例12：化合物69的合成
合成路线：
Figure PCTCN2017094481-appb-000050
化合物69的制备方法同实施例2，不同之处在于用中间体L替换中间体B。
元素分析结构(分子式C43H33NO)：理论值C,89.09；H,5.74；N,2.42；O,2.76；测试值：C,89.1；H,5.73；N,2.40；O,2.77。
HPLC-MS：材料分子量为579.73，实测分子量579.92。
实施例13：化合物73的合成
合成路线：
Figure PCTCN2017094481-appb-000051
化合物73的制备方法同实施例2，不同之处在于用中间体M替换中间体B。
元素分析结构(分子式C40H30N2O)：理论值C,86.61；H,5.45；N,5.05；O,2.88；测试值：C,86.6；H,5.46；N,5.07；O,2.87。HPLC-MS：材料分子量为554.68，实测分子量554.89。
实施例14：化合物83的合成
Figure PCTCN2017094481-appb-000052
化合物83的制备方法同实施例2，不同之处在于用中间体N替换中间体B。
元素分析结构(分子式C34H25NO2)：理论值C,85.15；H,5.25；N,2.92；O,6.67；测试值：C,85.17；H,5.24；N,2.93；O,6.66。HPLC-MS：材料分子量为479.57，实测分子量479.74。
实施例15：化合物92的合成
Figure PCTCN2017094481-appb-000053
化合物92的制备方法同实施例2，不同之处在于用中间体O替换中间体B。
元素分析结构(分子式C40H30N2O)：理论值C,86.61；H,5.45；N,5.05；O,2.88；测试值：C,86.65；H,5.44；N,5.05；O,2.86。HPLC-MS：材料分子量为554.68，实测分子量554.87。
实施例16：化合物96的合成
Figure PCTCN2017094481-appb-000054
化合物96的制备方法同实施例2，不同之处在于用中间体P替换中间体B。
元素分析结构(分子式C34H25NO2)：理论值C,85.15；H,5.25；N,2.92；O,6.67；测试值：C,85.18；H,5.25；N,2.92；O,6.65。
HPLC-MS：材料分子量为479.57，实测分子量479.81。
实施例17：化合物104的合成
Figure PCTCN2017094481-appb-000055
化合物104的制备方法同实施例1，不同之处在于用中间体Q替换中间体A。
元素分析结构(分子式C61H52N2O)：理论值C,88.37；H,6.32；N,3.38；O,1.93；测试值：C,88.38；H,6.31；N,3.40；O,1.91。
HPLC-MS：材料分子量为829.08，实测分子量829.27。
实施例18：化合物113的合成
Figure PCTCN2017094481-appb-000056
化合物113的制备方法同实施例2，不同之处在于用中间体R替换中间体B。
元素分析结构(分子式C41H30N2O3)：理论值C,82.25；H,5.05；N,4.68；O,8.02；测试值：C,82.26；H,5.04；N,4.67；O,8.03。HPLC-MS：材料分子量为598.69，实测分子量598.92。
实施例19：化合物117的合成
Figure PCTCN2017094481-appb-000057
化合物117的制备方法同实施例2，不同之处在于用中间体S替换中间体B。
元素分析结构(分子式C43H33NO2Se)：理论值C,76.55；H,4.93；N,2.08；O,4.74；Se,11.70；测试值：C,76.54；H,4.92；N,2.09；O,4.73；Se,11.72。HPLC-MS：材料分子量为674.69，实测分子量674.95。
实施例20：化合物144的合成
Figure PCTCN2017094481-appb-000058
化合物144的制备方法同实施例7，不同之处在于用中间体T替换中间体G。
元素分析结构(分子式C49H31N3O3)：理论值C,82.92；H,4.40；N,5.92；O,6.76；测试值：C,82.92；H,4.39；N,5.91；O,6.78。
HPLC-MS：材料分子量为709.79，实测分子量709.93。
实施例21：化合物149的合成
Figure PCTCN2017094481-appb-000059
化合物149的制备方法同实施例2，不同之处在于用中间体U替换中间体B。
元素分析结构(分子式C39H26N2O)：理论值C,86.96；H,4.87；N,5.20；O,2.97；测试值：C,86.99；H,4.86；N,5.19；O,2.96。
HPLC-MS：材料分子量为538.64，实测分子量538.82。
对本发明化合物进行理化特性表征，其中化合物3、17、63、96、136、149和现有材料CBP进行热性能、发光光谱及HOMO能级的测定，测试结果如表1所示。
表1
Figure PCTCN2017094481-appb-000060
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；λPL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；Φf是固体粉末荧光量子效率(利用美国海洋光学的Maya2000Pro光纤光谱仪，美国蓝菲公司的C-701积分球和海洋光学LLS-LED光源组成的测试固体荧光量子效率测试系统，参照文献Adv.Mater.1997，9，230-232的方法进行测定)；最高占据分子轨道HOMO能级是由光电子发射谱仪(AC-2型PESA)大气环境测试。
由上表数据可知，本发明化合物具有合适的HOMO、LUMO能级以及较高的热稳定性，适合作为发光层的主体材料；同时，本发明化合物具有合适的发光光谱，较高的Φf，使得应用本发明化合物作为掺杂材料的OLED器件效率和寿命得到提升。
以下通过实施例22～30和比较例1～3详细说明本发明合成的OLED材料在器件中作为发光层主体材料的应用效果。本发明所述23～30、比较例1～3与实施例22相比器件的制作工艺完全相同，并且所采用了相同的基板材料和电极材料，电极材料的膜厚也保持一致，所不同的是对器件中的发光层5的主体材料及掺杂材料做了变换。各实施例所得器件的结构组成如表2所示。所得器件的测试结果见表3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MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(化合物39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)/Al。相关材料的分子结构式如下所示：
Figure PCTCN2017094481-appb-000061
Figure PCTCN2017094481-appb-000062
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MoO3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1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，发光光谱以及器件的寿命。用同样的方法制备的器件实施例和比较例如表2所示；所得器件的测试结果见表3所示。
表2
Figure PCTCN2017094481-appb-000063
Figure PCTCN2017094481-appb-000064
表3
Figure PCTCN2017094481-appb-000065
Figure PCTCN2017094481-appb-000066
表2的器件制备方法和表3的测试结果表明：实施例22～24为本发明所述化合物作为发光层TADF主体材料应用于OLED发光器件制作；实施例26～27为本发明所述化合物作为发光层主体材料搭配TADF掺杂材料应用于OLED发光器件制作；实施例28～30为本发明所述化合物作为发光层Co-host材料搭配咔唑类主体材料应用于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比已知OLED材料获得较大提升。
以下通过实施例31～38和比较例4说明本发明合成的化合物在器件中作为发光层掺杂材料的应用效果。本发明所述31～38、比较例4与实施例22相比所述器件的制作工艺完全相同，并且所采用了相同的基板材料和电极材料，电极材料的膜厚也保持一致，所不同的是器件的传输层膜厚及发光层5中的掺杂材料不同，掺杂浓度变为7％。各器件的结构组成如表4所示。所得器件的测试结果见表5所示。
表4
Figure PCTCN2017094481-appb-000067
表5
Figure PCTCN2017094481-appb-000068
表5的结果表明：本发明所述化合物可作为发光层掺杂材料应用于OLED发光器件制作，并且与比较例4相比，无论是效率还是寿命均比已知OLED材料获得较大改观，特别是器件的驱动寿命获得较大的提升。
为了比较不同器件在高电流密度下效率衰减的情况，定义效率衰减系数
Figure PCTCN2017094481-appb-000069
进行表示，它表示驱动电流为100mA/cm2时器件的最大效率μ100与器件的最大效率μm之差与最大效率之间的比值，
Figure PCTCN2017094481-appb-000070
值越大，说明器件的效率滚降越严重，反之，说明器件在高电流密度下快速衰降的问题得到了控制。
本发明化合物可以作为发光层材料使用，对本发明化合物76、81、125和现有材料CBP制备器件分别进行效率衰减系数
Figure PCTCN2017094481-appb-000071
的测定，检测结果如表6所示。
表6
Figure PCTCN2017094481-appb-000072

Claims (11)

  1. 一种基于二芳基酮的化合物，其特征在于所述化合物的结构如通式(1)所示：
    Figure PCTCN2017094481-appb-100001
    其中，
    n＝1或2；
    Ar表示为苯基、萘基或联苯基；
    R1、R2分别独立的选取氢原子、苯基或通式(2)所示结构：
    Figure PCTCN2017094481-appb-100002
    其中，a为
    Figure PCTCN2017094481-appb-100003
    X1、X2分别独立的表示为氧原子、硫原子、硒原子、C1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基或芳基取代的叔胺基中的一种；a与CL1-CL2键、CL2-CL3键、CL3-CL4键、CL‘1-CL’2键、CL‘2-CL’3键或CL‘3-CL’4键连接。
  2. 根据权利要求1所述的基于二芳基酮的化合物，其特征在于R1、R2不同时为氢原子。
  3. 根据权利要求1所述的基于二芳基酮的化合物，其特征在于当R1、R2同时取苯基时，
    Figure PCTCN2017094481-appb-100004
    表示为：
    Figure PCTCN2017094481-appb-100005
  4. 根据权利要求1所述的基于二芳基酮的化合物，其特征在于当通式(2)的a取
    Figure PCTCN2017094481-appb-100006
    时，
    Figure PCTCN2017094481-appb-100007
    表示为：
    Figure PCTCN2017094481-appb-100008
    Figure PCTCN2017094481-appb-100009
    Figure PCTCN2017094481-appb-100010
    Figure PCTCN2017094481-appb-100011
  5. 根据权利要求1所述的基于二芳基酮的化合物，其特征在于当通式(2)的a取
    Figure PCTCN2017094481-appb-100012
    时，
    Figure PCTCN2017094481-appb-100013
    表示为：
    Figure PCTCN2017094481-appb-100014
  6. 根据权利要求1所述的基于二芳基酮的化合物，其特征在于当通式(2)的a取
    Figure PCTCN2017094481-appb-100015
    时，
    Figure PCTCN2017094481-appb-100016
    表示为：
    Figure PCTCN2017094481-appb-100017
    Figure PCTCN2017094481-appb-100018
    Figure PCTCN2017094481-appb-100019
    Figure PCTCN2017094481-appb-100020
    Figure PCTCN2017094481-appb-100021
    Figure PCTCN2017094481-appb-100022
    Figure PCTCN2017094481-appb-100023
    Figure PCTCN2017094481-appb-100024
  7. 根据权利要求1所述的基于二芳基酮的化合物，其特征在于当通式(2)的a取
    Figure PCTCN2017094481-appb-100025
    时，
    Figure PCTCN2017094481-appb-100026
    表示为：
    Figure PCTCN2017094481-appb-100027
  8. 根据权利要求1所述的基于二芳基酮的化合物，其特征在于所述化合物的具体结构式为：
    Figure PCTCN2017094481-appb-100028
    Figure PCTCN2017094481-appb-100029
    Figure PCTCN2017094481-appb-100030
    Figure PCTCN2017094481-appb-100031
    Figure PCTCN2017094481-appb-100032
    Figure PCTCN2017094481-appb-100033
    Figure PCTCN2017094481-appb-100034
    Figure PCTCN2017094481-appb-100035
    中的任一种。
  9. 一种制备权利要求1～8任一项所述基于二芳基酮的化合物的方法，其特征在于制备过程中的反应方程式是：
    n＝1时，
    Figure PCTCN2017094481-appb-100036
    具体制备过程为：
    称取溴代芳基酮和
    Figure PCTCN2017094481-appb-100037
    用甲苯溶解；再加入Pd2(dba)3、三叔丁基膦、叔丁醇钠；在惰性气氛下，将上述反应物的混合溶液于反应温度95～110℃，反应10～24小时，冷却并过滤反应溶液，滤液旋蒸，过硅胶柱，得到目标产物；
    所述溴代芳基酮与
    Figure PCTCN2017094481-appb-100038
    的摩尔比为1:1.2～3.0，Pd2(dba)3与溴代芳基酮的摩尔比为0.006～0.02:1，三叔丁基膦与溴代芳基酮的摩尔比为0.006～0.02:1，叔丁醇钠与溴代芳基酮的摩尔比为2.0～5.0:1。
  10. 一种含有权利要求1～8任一项所述基于二芳基酮的化合物的发光器件，其特征在于所述化合物作为发光层主体材料，应用于有机发光二极管。
  11. 一种含有权利要求1～8任一项所述基于二芳基酮的化合物的发光器件，其特征在于所述化合物作为发光层掺杂材料，应用于有机发光二极管。
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