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WO2018033086A1 - Dibenzo six-membered ring substituted compound having xanthone as core and applications thereof - Google Patents

Dibenzo six-membered ring substituted compound having xanthone as core and applications thereof Download PDF

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WO2018033086A1
WO2018033086A1 PCT/CN2017/097614 CN2017097614W WO2018033086A1 WO 2018033086 A1 WO2018033086 A1 WO 2018033086A1 CN 2017097614 W CN2017097614 W CN 2017097614W WO 2018033086 A1 WO2018033086 A1 WO 2018033086A1
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group
compound
xanthone
formula
substituted
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PCT/CN2017/097614
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French (fr)
Chinese (zh)
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徐凯
陈棪
李崇
张兆超
叶中华
张小庆
王立春
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江苏三月光电科技有限公司
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Publication of WO2018033086A1 publication Critical patent/WO2018033086A1/en

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    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
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    • C07D311/86—Oxygen atoms, e.g. xanthones
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Definitions

  • the present invention relates to the field of semiconductor technology, and in particular to a xanthone-based compound and its use as an luminescent layer material on an organic light emitting diode.
  • OLED Organic Light Emitting Diodes
  • OLED displays have self-luminous, wide viewing angle (above 175°), short reaction time, high luminous efficiency, and wide color. Domain, low operating voltage (3 ⁇ 10V), thin panel (less than 1mm) and can be curled.
  • OLED is hailed as a star flat display product in the 21st century. As the technology matures, it is likely to develop rapidly in the future, and the future is boundless.
  • OLED luminescence is that after applying an applied voltage, holes and electrons overcome the interface energy barrier, and are injected by the anode and the cathode, respectively entering the HOMO energy level of the hole transport layer and the LUMO energy level of the electron transport layer; and the post charge is added.
  • the electric field is driven to the interface between the hole transport layer and the electron transport layer, and the energy level difference of the interface causes the interface to accumulate charges; the electrons and holes recombine in the organic substance having the luminescent property to form an exciton.
  • This exciter is unstable in the general environment and will then release energy in the form of light or heat back to a stable ground state.
  • the excited state generated by recombination of electrons and holes is theoretically only 25% is a singlet excited state, and the remaining 75% is a triplet excited state, which will return to the ground state in the form of phosphorescence or heat.
  • OLEDs organic light-emitting diodes
  • conventional organic fluorescent materials can only emit light with 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). External quantum efficiency is generally less than 5%, which is far from the efficiency of phosphorescent devices.
  • the phosphorescent material enhances the intersystem crossing due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device is 100%.
  • 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 inter-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 present applicant provides a dibenzo six-membered ring-substituted compound having xanthone as a core and its use.
  • the oxaxanthone compound based on the TADF mechanism of the invention is applied as an luminescent layer material to an organic light emitting diode, and the OLED device using the compound of the invention has good photoelectric performance and can meet the requirements of the panel manufacturing enterprise.
  • the Applicant provides a compound having a xanthone as a core, the structure of which is as shown in the general formula (1):
  • R is represented by the general formula (2), the general formula (3), the general formula (4) or the general formula (5):
  • X 1 , Y are 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 substituted tertiary amine group.
  • R 1 is selected from the structure represented by the general formula (6)
  • R 2 is selected from the structure represented by the general formula (7):
  • a is X 2 and X 3 are each 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 substituted tertiary group.
  • One of the amine groups; a through the C L1 -C L2 bond, the C L2 -C L3 bond, the C L3 -C L4 bond, the C L4 -C L5 bond, the C L'1 -C L'2 bond, C L a '2 -C L'3 bond, a C L'3 -C L'4 bond or a C L'4 -C L'5 bond is attached to the formula (2) or the formula (4);
  • Ar 2 and Ar 3 are each independently represented by a phenyl group, a C 1-10 linear or branched alkyl substituted phenyl group, a diphenyl group, a terphenyl group, or a naphthyl group;
  • R 3 and R 4 are each independently represented by an alkyl group having 1 to 10 carbon atoms, an substituted or unsubstituted aryl group having 1 to 50 carbon atoms, an aryl group or an alkyl group having 1 to 50 carbon atoms.
  • the substituted, unsubstituted or unsubstituted carbon atom is a heteroaryl group of 1 to 50.
  • the R 3 and R 4 are each independently selected from the group consisting of an alkyl group having a carbon atom of 1-10, a phenyl group, a C 1-10 linear or branched alkyl group substituted phenyl group, a diphenyl group, a terphenyl group. a structure represented by a group, a naphthyl group, a formula (8), a formula (9), a formula (10) or a formula (11);
  • Ar 4 , Ar 5 and Ar 6 each independently represent a phenyl group, a C 1-10 linear or branched alkyl substituted phenyl group, a diphenyl group, a terphenyl group, a naphthyl group, and a C 1-10 straight
  • R 5 and R 6 are each independently selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 4 to 20 carbon atoms;
  • X 4 represents 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 substituted tertiary amine group.
  • the Ar is expressed as The structural formula of the compound is expressed as:
  • R is:
  • the specific structure of the xanthone-based compound is:
  • the Applicant also provides a light-emitting device comprising the compound as a light-emitting layer material for producing an organic electroluminescent device.
  • the compound is used as a host material of the light-emitting layer for producing an organic electroluminescent device.
  • the Applicant also provides a method of preparing the compound, the reaction equation occurring during the preparation is:
  • the reaction process of Formula 1 is as follows: weigh the brominated compound with the xanthone as the core and RH, and dissolve it with toluene; then add Pd 2 (dba) 3 , tri-tert-butylphosphine, sodium t-butoxide; under an inert atmosphere, The mixed solution of the above reactants is reacted at a reaction temperature of 95 to 110 ° C for 10 to 24 hours, and the reaction solution is cooled and filtered, and the filtrate is subjected to rotary distillation to pass through a silica gel column to obtain a target product;
  • the molar ratio of the bromide to the RH of the xanthone is 1:1.0-4.0; the molar ratio of the bromide of the Pd 2 (dba) 3 to the xanthone is 0.006-0.02:1, three The molar ratio of tert-butylphosphine to xanthone as the core bromide is 0.006 to 0.02:1, and the molar ratio of sodium t-butoxide to xanthone as the core bromide is 1.0 to 4.0:1;
  • the reaction process of Formula 2 is as follows: weigh the brominated compound with the xanthone as the core and Ar-B(OH) 2 , and dissolve it with toluene; then add Pd(PPh 3 ) 4 and sodium carbonate; under the inert atmosphere, the above The mixed solution of the reactants is reacted at a reaction temperature of 95 to 110 ° C for 10 to 24 hours, and the reaction solution is cooled and filtered, and the filtrate is rotary-screwed and passed through a silica gel column to obtain a target product;
  • the molar ratio of the bromide to the Ar-B(OH) 2 of the xanthone is 1:1.0-4.0; the molar ratio of the bromide of the Pd(PPh 3 ) 4 to the xanthone is 0.006. ⁇ 0.02:1, the molar ratio of sodium carbonate to xanthone as the core bromide is 1.0 to 4.0:1.
  • the compound of the invention uses xanthone as a mother core, destroys the crystallinity of the molecule, avoids the aggregation between molecules, and has good thermal stability; the structural molecule of the compound contains an electron donor (donor, D) and electrons.
  • the combination of receptors (A) can increase the orbital overlap, improve the luminous efficiency, and simultaneously connect the aromatic heterocyclic groups to obtain HOMO, LUMO spatially separated charge transfer state materials, and achieve the energy level difference between the small S1 state and the T1 state. Therefore, the reverse intersystem crossing is realized under the condition of thermal stimulation, and is suitable for use as a main material of the luminescent layer material.
  • the compound of the invention can be used as a host material of the light-emitting layer for the fabrication of the OLED light-emitting device, and obtains good device performance, and 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 obviously improved. .
  • the compound material of the invention has good application effect in the OLED light-emitting device and has good industrialization prospect.
  • Figure 1 is a schematic view showing the structure of a device applied to the compound of the present invention
  • 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 electrode layer.
  • HPLC-MS The material had a molecular weight of 634.19 and a molecular weight of 634.26.
  • HPLC-MS The molecular weight of the material was 762.32, and the measured molecular weight was 762.43.
  • HPLC-MS The material had a molecular weight of 533.24 and a molecular weight of 533.26.
  • HPLC-MS The material had a molecular weight of 686.29 and a molecular weight of 686.33.
  • HPLC-MS The material had a molecular weight of 631.25 and a molecular weight of 631.42.
  • HPLC-MS molecular weight of 755.28, measured molecular weight 755.29
  • HPLC-MS molecular weight of 711.25, measured molecular weight 711.40
  • HPLC-MS The molecular weight of the material was 937.37, and the measured molecular weight was 937.46.
  • HPLC-MS molecular weight of 826.28, measured molecular weight 826.36
  • HPLC-MS The material had a molecular weight of 838.36 and a molecular weight of 838.44.
  • HPLC-MS The material had a molecular weight of 796.31 and a molecular weight of 796.56.
  • HPLC-MS The material had a molecular weight of 811.32 and a molecular weight of 811.39.
  • HPLC-MS The material had a molecular weight of 734.29 and a molecular weight of 734.35.
  • HPLC-MS The material had a molecular weight of 786.25 and a molecular weight of 786.36.
  • HPLC-MS The material had a molecular weight of 686.29 and a molecular weight of 686.34.
  • HPLC-MS The material had a molecular weight of 619.18 and a molecular weight of 619.23.
  • HPLC-MS The molecular weight of the material was 1020.44, and the measured molecular weight was 1020.49.
  • HPLC-MS The material had a molecular weight of 840.32 and a molecular weight of 840.38.
  • the compound of the present invention can be used as a light-emitting layer material, and the thermal properties and HOMO levels of the compound C29, the compound C108 and the conventional material CBP of the present invention are measured, and the test results are shown in Table 1.
  • the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter, Germany), the heating rate is 10 ° C / min; the weight loss temperature Td is the temperature loss of 1% in the nitrogen atmosphere, The measurement was carried out on a TGA-50H thermogravimetric analyzer of Shimadzu Corporation, Japan, with a nitrogen flow rate of 20 mL/min; the highest occupied molecular orbital HOMO level and the lowest occupied molecular orbital LUMO level were determined by a photoelectron emission spectrometer (AC-2 type). Calculated by PESA) and UV spectrophotometer (UV) test, the test is atmospheric.
  • DSC differential scanning calorimetry
  • UV UV spectrophotometer
  • the compound of the present invention has high thermal stability, a suitable HOMO level, and is suitable as a light-emitting layer material; meanwhile, the compound of the present invention contains an electron donor (donor, D) and an electron acceptor (acceptor, A), the electrons and holes of the OLED device to which the compound of the present invention is applied are brought to an equilibrium state, so that device efficiency and lifetime are improved.
  • Examples 19-27 and Comparative Examples 1-3 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 19-27 and Comparative Examples 1-3.
  • Examples 19-27 Compared with Comparative Examples 1-3 the light-emitting layer materials of the devices of Comparative Examples 1-3 were conventional materials, and the device light-emitting layer body materials of Examples 19-27 were Inventive compound.
  • the structural composition of the device obtained in each example is shown in Table 2.
  • the performance test results of each device are shown in Table 3.
  • the molecular structure of each compound is as follows:
  • the transparent substrate layer 1 is made of a transparent material such as glass; the ITO anode layer 2 (having a film thickness of 150 nm) is washed, that is, sequentially washed with alkali, washed with pure water, dried, and then subjected to ultraviolet-ozone washing to remove the organic surface of the transparent ITO. the remains.
  • 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 formed, and the structure thereof comprises the material compound C22 used as the host material of the OLED light emitting layer 5, and GD-19 is used as a doping material, and the doping ratio of the doping material is
  • the film thickness of the light-emitting layer was 5% by weight.
  • the vacuum evaporation electron-transporting layer material was continued to be TPBI, and the vacuum-deposited film thickness of the 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 luminous efficiency, the luminescence spectrum, and the current-voltage characteristics of the device are measured.
  • the mixture was mixed in a weight ratio of 100:10, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).
  • the mixture was mixed in a weight ratio of 100:10, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).
  • the compound of the invention has good application effect as an luminescent layer material in an OLED light-emitting device, and has a good industrialization prospect.

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Abstract

Disclosed are a compound having xanthone as the core and applications thereof in an organic electroluminescent component. The compound has xanthone as the parent core and is connected to an aromatic heterocyclic group, thereby breaking molecular symmetry, thus breaking molecular crystallinity, preventing the effect of intermolecular aggregation, and providing great film-forming properties. The compound is applied as a light-emitting layer material on an organic light-emitting diode (OLED); an OLED component applied with the compound has great light-emitting properties and can satisfy demands of panel manufacturers.

Description

一种以氧杂蒽酮为核心的二苯并六元环取代化合物及其应用Dibenzo-6-membered ring substituted compound with xanthone as core and application thereof 技术领域Technical field
本发明涉及半导体技术领域，尤其是涉及一种基于氧杂蒽酮的化合物，以及其作为发光层材料在有机发光二极管上的应用。The present invention relates to the field of semiconductor technology, and in particular to a xanthone-based compound and its use as an luminescent layer material on an organic light emitting diode.
背景技术Background technique
有机发光二极管(OLED:Organic Light Emission Diodes)成为国内外非常热门的新兴平板显示器产品，这是因为OLED显示器具有自发光、广视角(达175°以上)、短反应时间、高发光效率、广色域、低工作电压(3～10V)、面板薄(可小于1mm)和可卷曲等特性。OLED被喻为21世纪的明星平面显示产品。随着技术越来越成熟，其今后有可能得到迅速发展，前途不可限量。Organic Light Emitting Diodes (OLED) has become a hot emerging flat panel display product at home and abroad. This is because OLED displays have self-luminous, wide viewing angle (above 175°), short reaction time, high luminous efficiency, and wide color. Domain, low operating voltage (3 ~ 10V), thin panel (less than 1mm) and can be curled. OLED is hailed as a star flat display product in the 21st century. As the technology matures, it is likely to develop rapidly in the future, and the future is boundless.
OLED发光的原理是通过施加一个外加电压，空穴和电子克服界面能障后,由阳极和阴极注入，分别进入空穴传送层的HOMO能阶和电子传送层的LUMO能阶；而后电荷在外加电场的驱动下传递至空穴传送层和电子传送层的界面，界面的能阶差使得界面会有电荷的累积；电子、空穴在有发光特性的有机物质内再结合，形成一个激发子，此激发子在一般环境是不稳定的，之后将以光或热的形式释放能量而回到稳定的基态。经由电子、空穴再结合产生的激发态理论上只有25％是单重激发态，其余75％为三重激发态，将以磷光或热的形式回归到基态。The principle of OLED luminescence is that after applying an applied voltage, holes and electrons overcome the interface energy barrier, and are injected by the anode and the cathode, respectively entering the HOMO energy level of the hole transport layer and the LUMO energy level of the electron transport layer; and the post charge is added. The electric field is driven to the interface between the hole transport layer and the electron transport layer, and the energy level difference of the interface causes the interface to accumulate charges; the electrons and holes recombine in the organic substance having the luminescent property to form an exciton. This exciter is unstable in the general environment and will then release energy in the form of light or heat back to a stable ground state. The excited state generated by recombination of electrons and holes is theoretically only 25% is a singlet excited state, and the remaining 75% is a triplet excited state, which will return to the ground state in the form of phosphorescence or heat.
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(△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。The use of organic light-emitting diodes (OLEDs) in large-area flat panel displays and illumination has attracted widespread attention in industry and academia. However, conventional organic fluorescent materials can only emit light with 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). External quantum efficiency is generally less than 5%, which is far from the efficiency of phosphorescent devices. Although the phosphorescent material enhances the intersystem crossing due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device is 100%. However, phosphorescent materials are expensive, the material stability is poor, and the efficiency of the device is seriously reduced, which limits its application in OLEDs. 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 (ΔE ST ), and triplet excitons can be converted into singlet exciton luminescence by inter-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%. At the same time, 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.
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。Although theoretically TADF materials can achieve 100% exciton utilization, there are actually the following problems: (1) The 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.
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。As far as the actual demand of the current OLED display lighting industry is concerned, the development of OLED materials is still far from enough. It is lagging behind the requirements of panel manufacturers, and it is especially important to develop higher performance organic functional materials as material enterprises.
发明内容Summary of the invention
针对现有技术存在的上述问题，本申请人提供了一种以氧杂蒽酮为核心的二苯并六元环取代化合物及其应用。本发明基于TADF机理的氧杂蒽酮类化合物作为发光层材料应用于有机发光二极管上，应用本发明化合物的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。In view of the above problems in the prior art, the present applicant provides a dibenzo six-membered ring-substituted compound having xanthone as a core and its use. The oxaxanthone compound based on the TADF mechanism of the invention is applied as an luminescent layer material to an organic light emitting diode, and the OLED device using the compound of the invention has good photoelectric performance and can meet the requirements of the panel manufacturing enterprise.
本发明的技术方案如下：The technical solution of the present invention is as follows:
本申请人提供了一种以氧杂蒽酮为核心的化合物，所述化合物的结构如通式(1)所示：The Applicant provides a compound having a xanthone as a core, the structure of which is as shown in the general formula (1):
Figure PCTCN2017097614-appb-000001
Figure PCTCN2017097614-appb-000001
三联苯基、萘基、蒽基或菲基；m、n分别独立的选取1或2；Terphenyl, naphthyl, anthracenyl or phenanthryl; m, n are independently selected 1 or 2;
通式(1)中
Figure PCTCN2017097614-appb-000002
表示(Ar)m连接在通式(1)两侧苯环上的任意碳原子上；In the general formula (1)
Figure PCTCN2017097614-appb-000002
Indicates that (Ar) m is attached to any carbon atom on the benzene ring on both sides of the formula (1);
R采用通式(2)、通式(3)、通式(4)或通式(5)表示： R is represented by the general formula (2), the general formula (3), the general formula (4) or the general formula (5):
Figure PCTCN2017097614-appb-000003
Figure PCTCN2017097614-appb-000003
其中，among them,
X1、Y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；X 1 , Y are 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 substituted tertiary amine group. a kind
R1选取通式(6)所示结构，R2选取通式(7)所示结构：R 1 is selected from the structure represented by the general formula (6), and R 2 is selected from the structure represented by the general formula (7):
Figure PCTCN2017097614-appb-000004
Figure PCTCN2017097614-appb-000004
a为
Figure PCTCN2017097614-appb-000005
X2、X3分别表示为氧原子、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通过CL1-CL2键、CL2-CL3键、CL3-CL4键、CL4-CL5键、CL‘1-CL’2键、CL‘2-CL’3键、CL‘3-CL’4键或CL‘4-CL’5键连接在通式(2)或通式(4)上；a is
Figure PCTCN2017097614-appb-000005
X 2 and X 3 are each 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 substituted tertiary group. One of the amine groups; a through the C L1 -C L2 bond, the C L2 -C L3 bond, the C L3 -C L4 bond, the C L4 -C L5 bond, the C L'1 -C L'2 bond, C L a '2 -C L'3 bond, a C L'3 -C L'4 bond or a C L'4 -C L'5 bond is attached to the formula (2) or the formula (4);
Ar2、Ar3分别独立的表示为苯基、C1-10直链或支链烷基取代的苯基、二联苯基、三联苯基、或萘基中的一种；Ar 2 and Ar 3 are each independently represented by a phenyl group, a C 1-10 linear or branched alkyl substituted phenyl group, a diphenyl group, a terphenyl group, or a naphthyl group;
R3、R4分别独立的表示为碳原子为1-10的烷基、取代或者未取代的碳原子为1-50的芳基、芳基或烷基取代的碳原子为1-50的胺基、取代或者未取代的碳原子为1-50的杂芳基。R 3 and R 4 are each independently represented by an alkyl group having 1 to 10 carbon atoms, an substituted or unsubstituted aryl group having 1 to 50 carbon atoms, an aryl group or an alkyl group having 1 to 50 carbon atoms. The substituted, unsubstituted or unsubstituted carbon atom is a heteroaryl group of 1 to 50.
优选的，所述R3、R4分别独立的选取碳原子为1-10的烷基、苯基、C1-10直链或支链烷基取代的苯基、二联苯基、三联苯基、萘基、通式(8)、通式(9)、通式(10)或通式(11)所示结构；Preferably, the R 3 and R 4 are each independently selected from the group consisting of an alkyl group having a carbon atom of 1-10, a phenyl group, a C 1-10 linear or branched alkyl group substituted phenyl group, a diphenyl group, a terphenyl group. a structure represented by a group, a naphthyl group, a formula (8), a formula (9), a formula (10) or a formula (11);
Figure PCTCN2017097614-appb-000006
Figure PCTCN2017097614-appb-000006
其中，Ar4、Ar5、Ar6分别独立的表示苯基、C1-10直链或支链烷基取代的苯基、二联苯基、三联苯基、萘基、C1-10直链或支链烷基取代的苯并呋喃基、C1-10直链或支链烷基取代的苯并噻吩基、C1-10直链或支链烷基取代的芴基、C1-10直链 或支链烷基取代的咔唑基中的一种；Wherein, Ar 4 , Ar 5 and Ar 6 each independently represent a phenyl group, a C 1-10 linear or branched alkyl substituted phenyl group, a diphenyl group, a terphenyl group, a naphthyl group, and a C 1-10 straight A chain or branched alkyl substituted benzofuranyl group, a C 1-10 straight or branched alkyl substituted benzothienyl group, a C 1-10 straight or branched alkyl substituted fluorenyl group, C 1- One of 10 linear or branched alkyl substituted oxazolyl groups;
R5、R6分别独立的选取氢、碳原子为1-10的烷基、或碳原子为4-20的芳香基；R 5 and R 6 are each independently selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 4 to 20 carbon atoms;
X4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。X 4 represents 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 substituted tertiary amine group. One.
优选的，所述Ar表示为
Figure PCTCN2017097614-appb-000007
时，所述化合物的结构通式表示为：Preferably, the Ar is expressed as
Figure PCTCN2017097614-appb-000007
The structural formula of the compound is expressed as:
Figure PCTCN2017097614-appb-000008
Figure PCTCN2017097614-appb-000008
中的任一种。Any of them.
优选的，所述Ar表示为R时，所述化合物的结构通式表示为：Preferably, when Ar is represented by R, the structural formula of the compound is expressed as:
Figure PCTCN2017097614-appb-000009
Figure PCTCN2017097614-appb-000009
Figure PCTCN2017097614-appb-000010
Figure PCTCN2017097614-appb-000010
中的任一种。Any of them.
优选的，所述通式(1)中R为：Preferably, in the formula (1), R is:
Figure PCTCN2017097614-appb-000011
Figure PCTCN2017097614-appb-000011
Figure PCTCN2017097614-appb-000012
Figure PCTCN2017097614-appb-000012
Figure PCTCN2017097614-appb-000013
Figure PCTCN2017097614-appb-000013
Figure PCTCN2017097614-appb-000014
Figure PCTCN2017097614-appb-000014
Figure PCTCN2017097614-appb-000015
Figure PCTCN2017097614-appb-000015
中的任一种。Any of them.
优选的，所述基于氧杂蒽酮的化合物的具体结构为：Preferably, the specific structure of the xanthone-based compound is:
Figure PCTCN2017097614-appb-000016
Figure PCTCN2017097614-appb-000016
Figure PCTCN2017097614-appb-000017
Figure PCTCN2017097614-appb-000017
Figure PCTCN2017097614-appb-000018
Figure PCTCN2017097614-appb-000018
Figure PCTCN2017097614-appb-000019
Figure PCTCN2017097614-appb-000019
Figure PCTCN2017097614-appb-000020
Figure PCTCN2017097614-appb-000020
Figure PCTCN2017097614-appb-000021
Figure PCTCN2017097614-appb-000021
Figure PCTCN2017097614-appb-000022
Figure PCTCN2017097614-appb-000022
Figure PCTCN2017097614-appb-000023
Figure PCTCN2017097614-appb-000023
Figure PCTCN2017097614-appb-000024
Figure PCTCN2017097614-appb-000024
C121中的任一种。Any of C121.
本申请人还提供了一种包含所述化合物的发光器件，所述化合物作为发光层材料，用于制作有机电致发光器件。The Applicant also provides a light-emitting device comprising the compound as a light-emitting layer material for producing an organic electroluminescent device.
优选的，所述化合物作为发光层的主体材料，用于制作有机电致发光器件。Preferably, the compound is used as a host material of the light-emitting layer for producing an organic electroluminescent device.
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：The Applicant also provides a method of preparing the compound, the reaction equation occurring during the preparation is:
Figure PCTCN2017097614-appb-000025
Figure PCTCN2017097614-appb-000025
式1反应过程如下：称取氧杂蒽酮为核心的溴代化合物和R-H，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、过滤反应溶液，滤液旋 蒸，过硅胶柱，得到目标产物；The reaction process of Formula 1 is as follows: weigh the brominated compound with the xanthone as the core and RH, and dissolve it with toluene; then add Pd 2 (dba) 3 , tri-tert-butylphosphine, sodium t-butoxide; under an inert atmosphere, The mixed solution of the above reactants is reacted at a reaction temperature of 95 to 110 ° C for 10 to 24 hours, and the reaction solution is cooled and filtered, and the filtrate is subjected to rotary distillation to pass through a silica gel column to obtain a target product;
所述氧杂蒽酮为核心的溴化物与R-H的摩尔比为1:1.0～4.0；Pd2(dba)3与氧杂蒽酮为核心的溴化物的摩尔比为0.006～0.02:1，三叔丁基膦与氧杂蒽酮为核心的溴化物的摩尔比为0.006～0.02:1，叔丁醇钠与氧杂蒽酮为核心的溴化物的摩尔比为1.0～4.0:1；The molar ratio of the bromide to the RH of the xanthone is 1:1.0-4.0; the molar ratio of the bromide of the Pd 2 (dba) 3 to the xanthone is 0.006-0.02:1, three The molar ratio of tert-butylphosphine to xanthone as the core bromide is 0.006 to 0.02:1, and the molar ratio of sodium t-butoxide to xanthone as the core bromide is 1.0 to 4.0:1;
式2反应过程如下：称取氧杂蒽酮为核心的溴代化合物和Ar-B(OH)2，用甲苯溶解；再加入Pd(PPh3)4、碳酸钠；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、过滤反应溶液，滤液旋蒸，过硅胶柱，得到目标产物；The reaction process of Formula 2 is as follows: weigh the brominated compound with the xanthone as the core and Ar-B(OH) 2 , and dissolve it with toluene; then add Pd(PPh 3 ) 4 and sodium carbonate; under the inert atmosphere, the above The mixed solution of the reactants is reacted at a reaction temperature of 95 to 110 ° C for 10 to 24 hours, and the reaction solution is cooled and filtered, and the filtrate is rotary-screwed and passed through a silica gel column to obtain a target product;
所述氧杂蒽酮为核心的溴化物与Ar-B(OH)2的摩尔比为1:1.0～4.0；Pd(PPh3)4与氧杂蒽酮为核心的溴化物的摩尔比为0.006～0.02:1，碳酸钠与氧杂蒽酮为核心的溴化物的摩尔比为1.0～4.0:1。The molar ratio of the bromide to the Ar-B(OH) 2 of the xanthone is 1:1.0-4.0; the molar ratio of the bromide of the Pd(PPh 3 ) 4 to the xanthone is 0.006. ～0.02:1, the molar ratio of sodium carbonate to xanthone as the core bromide is 1.0 to 4.0:1.
本发明有益的技术效果在于：The beneficial technical effects of the present invention are:
本发明化合物以氧杂蒽酮为母核，破坏分子的结晶性，避免了分子间的聚集作用，具有良好的热稳定性；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，同时连接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，适合作为发光层材料主材料使用。The compound of the invention uses xanthone as a mother core, destroys the crystallinity of the molecule, avoids the aggregation between molecules, and has good thermal stability; the structural molecule of the compound contains an electron donor (donor, D) and electrons. The combination of receptors (A) can increase the orbital overlap, improve the luminous efficiency, and simultaneously connect the aromatic heterocyclic groups to obtain HOMO, LUMO spatially separated charge transfer state materials, and achieve the energy level difference between the small S1 state and the T1 state. Therefore, the reverse intersystem crossing is realized under the condition of thermal stimulation, and is suitable for use as a main material of the luminescent layer material.
本发明所述化合物可作为发光层主体材料应用于OLED发光器件制作，获得了良好的器件表现，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。The compound of the invention can be used as a host material of the light-emitting layer for the fabrication of the OLED light-emitting device, and obtains good device performance, and 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 obviously improved. . The compound material of the invention has good application effect in the OLED light-emitting device and has good industrialization prospect.
附图说明DRAWINGS
图1为本发明化合物应用的器件结构示意图；Figure 1 is a schematic view showing the structure of a device applied to the compound of the present invention;
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为阴极电极层。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, 6 is an electron transport layer, 7 is an electron injection layer, and 8 is a cathode electrode layer. .
具体实施方式detailed description
下面结合附图和实施例，对本发明进行具体描述。The present invention will be specifically described below in conjunction with the accompanying drawings and embodiments.
实施例1化合物C01的合成 Synthesis of Compound C01 of Example 1
Figure PCTCN2017097614-appb-000026
Figure PCTCN2017097614-appb-000026
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 2-溴-氧杂蒽酮，0.015mol化合物A1，0.03mol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99.30％，收率36.80％。A 250 ml four-necked flask was charged with 0.01 mol of 2-bromo-xanthone, 0.015 mol of compound A1, 0.03 mol of sodium t-butoxide, and 1 × 10 -4 mol of Pd 2 (dba) 3 under a nitrogen atmosphere. , 1 × 10 -4 mol of tri-tert-butylphosphine, 150 ml of toluene, heated under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, the filtrate is steamed, passed through a silica gel column to obtain the target product, the purity is 99.30%, The rate is 36.80%.
HPLC-MS：材料分子量为634.19，实测分子量634.26。HPLC-MS: The material had a molecular weight of 634.19 and a molecular weight of 634.26.
实施例2化合物C12的合成Synthesis of Compound C12 of Example 2
Figure PCTCN2017097614-appb-000027
Figure PCTCN2017097614-appb-000027
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3-(3-溴苯基)-氧杂蒽酮，0.015molA2，0.03mol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97.56％，收率45.65％。A 250 ml four-necked flask was charged with 0.01 mol of 3-(3-bromophenyl)-xanthone, 0.015 mol of A2, 0.03 mol of sodium t-butoxide, and 1 × 10 -4 mol of Pd 2 under a nitrogen atmosphere. (dba) 3 , 1 × 10 -4 mol of tri-tert-butylphosphine, 150 ml of toluene, heated under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, and the filtrate is steamed, passed through a silica gel column to obtain the desired product, purity 97.56%, the yield was 45.65%.
HPLC-MS：材料分子量为762.32，实测分子量762.43。HPLC-MS: The molecular weight of the material was 762.32, and the measured molecular weight was 762.43.
实施例3化合物C22的合成Synthesis of Compound C22 of Example 3
Figure PCTCN2017097614-appb-000028
Figure PCTCN2017097614-appb-000028
500ml的四口瓶，在通入氮气的气氛下，加入0.01mo 2-溴氧杂蒽酮，0.015molA3，用混合溶剂溶解(180ml甲苯，90ml乙醇)，然后加入0.03mol Na2CO3水溶液(2M)，然后加入0.0001mol Pd(PPh3)4，加热回流10-24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，HPLC纯度99.40％，收率56.00％。 A 500-ml four-necked flask was charged with 0.01 mol of 2-bromoxanthone, 0.015 mol of A3 under a nitrogen atmosphere, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol), and then 0.03 mol of an aqueous solution of Na 2 CO 3 was added ( 2M), then 0.0001 mol of Pd(PPh 3 ) 4 was added , and the mixture was heated under reflux for 10-24 hours, and the plate was sampled and the reaction was completed. It was naturally cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to give the desired product. The HPLC purity was 99.40% and the yield was 56.00%.
HPLC-MS：材料分子量为533.24，实测分子量533.26。HPLC-MS: The material had a molecular weight of 533.24 and a molecular weight of 533.26.
实施例4化合物C26的合成Synthesis of Compound C26 of Example 4
Figure PCTCN2017097614-appb-000029
Figure PCTCN2017097614-appb-000029
500ml的四口瓶，在通入氮气的气氛下，加入0.01mo 2-溴氧杂蒽酮，0.015molA4，用混合溶剂溶解(180ml甲苯，90ml乙醇)，然后加入0.03mol Na2CO3水溶液(2M)，然后加入0.0001mol Pd(PPh3)4，加热回流10-24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，HPLC纯度99.80％，收率38.00％。A 500-ml four-necked flask was charged with 0.01 mol of 2-bromoxanthone, 0.015 mol of A4 under a nitrogen atmosphere, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol), and then 0.03 mol of an aqueous solution of Na 2 CO 3 was added ( 2M), then 0.0001 mol of Pd(PPh 3 ) 4 was added , and the mixture was heated under reflux for 10-24 hours, and the plate was sampled and the reaction was completed. It was naturally cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to give the desired product. The HPLC purity was 99.80% and the yield was 38.00%.
HPLC-MS：材料分子量为686.29，实测分子量686.33。HPLC-MS: The material had a molecular weight of 686.29 and a molecular weight of 686.33.
实施例5化合物C29的合成Synthesis of Compound C29 of Example 5
Figure PCTCN2017097614-appb-000030
Figure PCTCN2017097614-appb-000030
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol3-(4-溴苯基)-氧杂蒽酮，0.015mol9,9-二甲基-2,7-二苯基-9,10-二氢吖啶，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97.86％，收率68.40％。A 250 ml four-necked flask was charged with 0.01 mol of 3-(4-bromophenyl)-xanthone and 0.015 mol of 9,9-dimethyl-2,7-diphenyl-9 under a nitrogen atmosphere. 10-dihydroacridine, 0.03 mol of sodium t-butoxide, 1 × 10 -4 mol Pd 2 (dba) 3 , 1 × 10 -4 mol of tri-tert-butylphosphine, 150 ml of toluene, heated under reflux for 24 hours, sampling plate The reaction is complete, natural cooling, filtration, and the filtrate is steamed and passed through a silica gel column to obtain the target product, the purity is 97.86%, and the yield is 68.40%.
HPLC-MS：材料分子量为631.25，实测分子量631.42。HPLC-MS: The material had a molecular weight of 631.25 and a molecular weight of 631.42.
实施例6化合物C30的合成Synthesis of Compound C30 of Example 6
Figure PCTCN2017097614-appb-000031
Figure PCTCN2017097614-appb-000031
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol2-(4-溴苯基)-氧杂蒽酮，0.015mol 3,6,9,9-四苯基-9,10-二氢吖啶，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98.68％，收率48.40％。A 250 ml four-necked flask was charged with 0.01 mol of 2-(4-bromophenyl)-xanthone, 0.015 mol of 3,6,9,9-tetraphenyl-9,10-di under a nitrogen atmosphere. Hydrogen acridine, 0.03 mol sodium t-butoxide, 1 × 10 -4 mol Pd 2 (dba) 3 , 1 × 10 -4 mol tri-tert-butylphosphine, 150 ml of toluene, heated under reflux for 24 hours, sampling plate, complete reaction , natural cooling, filtration, rotary distillation of the filtrate, through a silica gel column, to obtain the desired product, purity 98.68%, yield 48.40%.
HPLC-MS：材料分子量为755.28，实测分子量755.29HPLC-MS: molecular weight of 755.28, measured molecular weight 755.29
实施例7化合物C37的合成Synthesis of Compound C37 of Example 7
Figure PCTCN2017097614-appb-000032
Figure PCTCN2017097614-appb-000032
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol2-溴氧杂蒽酮，0.015molN,N,N',N'-四苯基-10H-吩恶嗪-3,7-二胺基，0.03mol叔丁醇钠，1×10-4molPd2(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99.81％，收率56.50％。A 250 ml four-necked flask was charged with 0.01 mol of 2-bromo xanthone, 0.015 mol of N,N', N'-tetraphenyl-10H-phenoxazin-3,7-di under a nitrogen atmosphere. Amine, 0.03 mol of sodium t-butoxide, 1 × 10 -4 mol of Pd 2 (dba) 3 , 1 × 10 -4 mol of tri-tert-butylphosphine, 150 ml of toluene, heated under reflux for 24 hours, sampling the plate, the reaction is complete, natural The mixture was cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to afford the desired product, purity 99.81%, yield 56.50%.
HPLC-MS：材料分子量为711.25，实测分子量711.40HPLC-MS: molecular weight of 711.25, measured molecular weight 711.40
实施例8化合物C41的合成Synthesis of Compound C of Example 8
Figure PCTCN2017097614-appb-000033
Figure PCTCN2017097614-appb-000033
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol3-(4-溴苯基)-氧杂蒽酮，0.015mol 9,9,N,N,N',N'-六苯基-9H,10H-吖啶-3,6-二胺，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99.10％，收率43.80％。A 250 ml four-necked flask was charged with 0.01 mol of 3-(4-bromophenyl)-xanthone, 0.015 mol of 9,9,N,N,N',N'-hexaphenyl under a nitrogen atmosphere. -9H,10H-acridine-3,6-diamine, 0.03 mol sodium t-butoxide, 1×10 -4 mol Pd 2 (dba) 3 , 1×10 −4 mol tri-tert-butylphosphine, 150 ml toluene, The mixture was heated under reflux for 24 hours, and the plate was sampled, and the reaction was completed, and the mixture was cooled, filtered, and the filtrate was evaporated to dryness to afford the desired product, purity 99.10%, yield 43.80%.
HPLC-MS：材料分子量为937.37，实测分子量937.46HPLC-MS: The molecular weight of the material was 937.37, and the measured molecular weight was 937.46.
实施例9化合物C47的合成 Synthesis of Compound C47 of Example 9
Figure PCTCN2017097614-appb-000034
Figure PCTCN2017097614-appb-000034
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol3-(4-溴苯基)-氧杂蒽酮，0.015mol二-(二苯并呋喃)-(9,9-二甲基-9,10-二氢-吖啶-2-基)-胺，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99.80％，收率32.20％。In a 250 ml four-necked flask, 0.01 mol of 3-(4-bromophenyl)-xanthone and 0.015 mol of bis-(dibenzofuran)-(9,9-dimethyl group) were added under a nitrogen atmosphere. -9,10-dihydro-acridin-2-yl)-amine, 0.03 mol of sodium t-butoxide, 1 × 10 -4 mol of Pd 2 (dba) 3 , 1 × 10 -4 mol of tri-tert-butylphosphine, 150 ml of toluene, heating under reflux for 24 hours, sampling the plate, the reaction was completed, naturally cooled, filtered, and the filtrate was rotary-screwed and passed through a silica gel column to obtain the desired product, purity 99.80%, yield 32.20%.
HPLC-MS：材料分子量为826.28，实测分子量826.36HPLC-MS: molecular weight of 826.28, measured molecular weight 826.36
实施例10化合物C49的合成Synthesis of Compound C49 of Example 10
Figure PCTCN2017097614-appb-000035
Figure PCTCN2017097614-appb-000035
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol2-溴氧杂蒽酮，0.015mol A5，0.03mol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98.25％，收率46.50％。A 250 ml four-necked flask was charged with 0.01 mol of 2-bromo xanthone, 0.015 mol of A5, 0.03 mol of sodium t-butoxide, 1 × 10 -4 mol of Pd 2 (dba) 3 , 1 × under a nitrogen atmosphere. 10 -4 mol of tri-tert-butylphosphine, 150 ml of toluene, heating under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, and the filtrate is steamed and passed through a silica gel column to obtain the desired product, purity 98.25%, yield 46.50% .
HPLC-MS：材料分子量为838.36，实测分子量838.44。HPLC-MS: The material had a molecular weight of 838.36 and a molecular weight of 838.44.
实施例11化合物C55的合成Synthesis of Compound C55 of Example 11
Figure PCTCN2017097614-appb-000036
Figure PCTCN2017097614-appb-000036
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol3-(4-溴苯基)-氧杂蒽酮，0.015mol 2-(3,6-二苯基-咔唑-9-基)-9,9-二甲基-9,10-二氢吖啶，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97.78％，收率55.90％。 A 250 ml four-necked flask was charged with 0.01 mol of 3-(4-bromophenyl)-xanthone and 0.015 mol of 2-(3,6-diphenyl-oxazol-9-yl group under a nitrogen atmosphere. -9,9-Dimethyl-9,10-dihydroacridine, 0.03 mol of sodium t-butoxide, 1 × 10 -4 mol Pd 2 (dba) 3 , 1 × 10 -4 mol of tri-tert-butylphosphine 150 ml of toluene, heated under reflux for 24 hours, sampled the plate, the reaction was completed, naturally cooled, filtered, and the filtrate was rotary-screwed and passed through a silica gel column to obtain the desired product. The purity was 97.78%, and the yield was 55.90%.
HPLC-MS：材料分子量为796.31，实测分子量796.56。HPLC-MS: The material had a molecular weight of 796.31 and a molecular weight of 796.56.
实施例12化合物C63的合成Synthesis of Compound C63 of Example 12
Figure PCTCN2017097614-appb-000037
Figure PCTCN2017097614-appb-000037
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol3-(4-溴苯基)-氧杂蒽酮，0.015mol(7-咔唑-9-基-9,9-二甲基-9,10-二氢-吖啶-2-基)-二苯基胺，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99.20％，收率46.30％。In a 250 ml four-necked flask, 0.01 mol of 3-(4-bromophenyl)-xanthone and 0.015 mol (7-carbazole-9-yl-9,9-dimethyl group) were added under a nitrogen atmosphere. -9,10-Dihydro-acridin-2-yl)-diphenylamine, 0.03 mol of sodium t-butoxide, 1×10 -4 mol Pd 2 (dba) 3 , 1×10 -4 mol tri-tert-butyl Base phosphine, 150 ml of toluene, heated under reflux for 24 hours, sampled the plate, the reaction was completed, naturally cooled, filtered, and the filtrate was rotary-screwed and passed through a silica gel column to obtain the desired product, purity 99.20%, yield 46.30%.
HPLC-MS：材料分子量为811.32，实测分子量811.39。HPLC-MS: The material had a molecular weight of 811.32 and a molecular weight of 811.39.
实施例13化合物C70的合成Synthesis of Compound C70 of Example 13
Figure PCTCN2017097614-appb-000038
Figure PCTCN2017097614-appb-000038
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 2-(3-溴苯基)-氧杂蒽酮，0.015mol 9,9-二甲基-3-(6-甲基-9-苯基-9H-咔唑-3-基)-9,10-二氢吖啶，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99.59％，收率65.70％。A 250 ml four-necked flask was charged with 0.01 mol of 2-(3-bromophenyl)-xanthone, 0.015 mol of 9,9-dimethyl-3-(6-methyl- under a nitrogen atmosphere. 9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine, 0.03 mol of sodium t-butoxide, 1 × 10 -4 mol Pd 2 (dba) 3 , 1 × 10 -4 mol Tri-tert-butylphosphine, 150 ml of toluene, heated under reflux for 24 hours, sampled the plate, the reaction was completed, naturally cooled, filtered, and the filtrate was rotary-screwed and passed through a silica gel column to obtain the desired product. The purity was 99.59% and the yield was 65.70%.
HPLC-MS：材料分子量为734.29，实测分子量734.35。HPLC-MS: The material had a molecular weight of 734.29 and a molecular weight of 734.35.
实施例14化合物C92的合成Synthesis of Compound C92 of Example 14
Figure PCTCN2017097614-appb-000039
Figure PCTCN2017097614-appb-000039
500ml的四口瓶，在通入氮气的气氛下，加入0.01mo 2-(4-溴苯基)-氧杂蒽酮，0.015molA6，用混合溶剂溶解(180ml甲苯，90ml乙醇)，然后加入0.03molNa2CO3水溶液(2M)，然后加入0.0001mol Pd(PPh3)4，加热回流10-24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，HPLC纯度95.80％，收率43.50％。A 500-ml four-necked flask was charged with 0.01 mol of 2-(4-bromophenyl)-xanthone, 0.015 mol of A6, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol), and then added to 0.03. A solution of molNa 2 CO 3 (2 M), then 0.0001 mol of Pd(PPh 3 ) 4 was added , and the mixture was heated under reflux for 10-24 hours, and the plate was sampled and the reaction was completed. It was naturally cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to give the desired product. The HPLC purity was 95.80% and the yield was 43.50%.
HPLC-MS：材料分子量为786.25，实测分子量786.36。HPLC-MS: The material had a molecular weight of 786.25 and a molecular weight of 786.36.
实施例15化合物C101的合成Synthesis of Compound C101 of Example 15
Figure PCTCN2017097614-appb-000040
Figure PCTCN2017097614-appb-000040
500ml的四口瓶，在通入氮气的气氛下，加入0.01mo 2-溴-氧杂蒽酮，0.015molA7，用混合溶剂溶解(180ml甲苯，90ml乙醇)，然后加入0.03molNa2CO3水溶液(2M)，然后加入0.0001mol Pd(PPh3)4，加热回流10-24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，HPLC纯度99.70％，收率56.50％。A 500-ml four-necked flask was charged with 0.01 mol of 2-bromo-xanthone, 0.015 mol of A7 under a nitrogen atmosphere, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol), and then added with 0.03 mol of an aqueous solution of Na 2 CO 3 ( 2M), then 0.0001 mol of Pd(PPh 3 ) 4 was added , and the mixture was heated under reflux for 10-24 hours, and the plate was sampled and the reaction was completed. It was naturally cooled, filtered, and the filtrate was evaporated to dryness. The title compound was obtained from the silica gel column. The HPLC purity was 99.70%, yield 56.50%.
HPLC-MS：材料分子量为686.29，实测分子量686.34。HPLC-MS: The material had a molecular weight of 686.29 and a molecular weight of 686.34.
实施例16化合物C108的合成Synthesis of Compound 16 of Example 16
Figure PCTCN2017097614-appb-000041
Figure PCTCN2017097614-appb-000041
500ml的四口瓶，在通入氮气的气氛下，加入0.01mo 2-溴-氧杂蒽酮，0.015molA8，用混合溶剂溶解(180ml甲苯，90ml乙醇)，然后加入0.03molNa2CO3水溶液(2M)，然后加入0.0001mol Pd(PPh3)4，加热回流10-24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，HPLC纯度99.20％，收率32.90％。A 500-ml four-necked flask was charged with 0.01 mol of 2-bromo-xanthone, 0.015 mol of A8 under a nitrogen atmosphere, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol), and then added with 0.03 mol of an aqueous solution of Na 2 CO 3 ( 2M), then 0.0001 mol of Pd(PPh 3 ) 4 was added , and the mixture was heated under reflux for 10-24 hours, and the plate was sampled and the reaction was completed. It was naturally cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to afford the desired product. The HPLC purity was 99.20% and the yield was 32.90%.
HPLC-MS：材料分子量为619.18，实测分子量619.23。HPLC-MS: The material had a molecular weight of 619.18 and a molecular weight of 619.23.
实施例17化合物C116的合成 Example 17 Synthesis of Compound C116
Figure PCTCN2017097614-appb-000042
Figure PCTCN2017097614-appb-000042
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 2-(3,5-二溴苯基)-氧杂蒽酮，0.03mol(9,9-二甲基-9,10-二氢-吖啶-3-基)-二苯基胺，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98.56％，收率49.50％。A 250 ml four-necked flask was charged with 0.01 mol of 2-(3,5-dibromophenyl)-xanthone, 0.03 mol (9,9-dimethyl-9,10- under a nitrogen atmosphere). dihydro - acridine-3-yl) - diphenylamine, 0.03mol sodium tert-butoxide, 1 × 10 -4 mol Pd 2 (dba) 3, 1 × 10 -4 mol butylphosphine, 150ml toluene The mixture was heated under reflux for 24 hours, and the spot plate was sampled, the reaction was completed, the mixture was naturally cooled, filtered, and the filtrate was rotary-screwed, and passed through a silica gel column to obtain the target product, purity 98.56%, yield 49.50%.
HPLC-MS：材料分子量为1020.44，实测分子量1020.49。HPLC-MS: The molecular weight of the material was 1020.44, and the measured molecular weight was 1020.49.
实施例18化合物C117的合成Synthesis of Compound 18 of Example 18
Figure PCTCN2017097614-appb-000043
Figure PCTCN2017097614-appb-000043
500ml的四口瓶，在通入氮气的气氛下，加入0.01mo 2-(3,5-二溴苯基)-氧杂蒽酮，0.015molA9，用混合溶剂溶解(180ml甲苯，90ml乙醇)，然后加入0.03molNa2CO3水溶液(2M)，然后加入0.0001mol Pd(PPh3)4，加热回流10-24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，HPLC纯度97.50％，收率29.60％。A 500-ml four-necked flask was charged with 0.01 mol of 2-(3,5-dibromophenyl)-xanthone, 0.015 mol of A9, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol) under a nitrogen atmosphere. Then, 0.03 mol of an aqueous solution of Na 2 CO 3 (2 M) was added, and then 0.0001 mol of Pd(PPh 3 ) 4 was added , and the mixture was heated under reflux for 10 to 24 hours, and the plate was sampled, and the reaction was completed. It was naturally cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to afford the desired product. The HPLC purity was 97.50%, and the yield was 29.60%.
HPLC-MS：材料分子量为840.32，实测分子量840.38。HPLC-MS: The material had a molecular weight of 840.32 and a molecular weight of 840.38.
本发明化合物可以作为发光层材料使用，对本发明化合物C29、化合物C108和现有材料CBP分别进行热性能、HOMO能级的测定，检测结果如表1所示。The compound of the present invention can be used as a light-emitting layer material, and the thermal properties and HOMO levels of the compound C29, the compound C108 and the conventional material CBP of the present invention are measured, and the test results are shown in Table 1.
表1Table 1
化合物Compound Tg(℃)Tg (°C) Td(℃)Td (°C) HOMO能级(eV)HOMO level (eV) 功用function
化合物C29Compound C29 130130 410410 -5.65-5.65 主体材料Body material
化合物C108Compound C108 138138 389389 -5.73-5.73 主体材料Body material
化合物CBPCompound CBP 113113 353353 -5.90-5.90 主体材料Body material
注：玻璃化温度Tg由示差扫描量热法(DSC，德国耐驰公司DSC204F1示差扫描量热仪)测定，升温速率10℃/min；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；最高占据分子轨道HOMO能级及最低占据分子轨道LUMO能级是由光电子发射谱仪(AC-2型PESA)、以及紫外分光光度计(UV)测试计算所得，测试为大气环境。Note: The glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter, Germany), the heating rate is 10 ° C / min; the weight loss temperature Td is the temperature loss of 1% in the nitrogen atmosphere, The measurement was carried out on a TGA-50H thermogravimetric analyzer of Shimadzu Corporation, Japan, with a nitrogen flow rate of 20 mL/min; the highest occupied molecular orbital HOMO level and the lowest occupied molecular orbital LUMO level were determined by a photoelectron emission spectrometer (AC-2 type). Calculated by PESA) and UV spectrophotometer (UV) test, the test is atmospheric.
由上表数据可知，本发明化合物具有较高的热稳定性，适当的HOMO能级，适合作为发光层材料；同时，本发明化合物含有电子给体(donor,D)与电子受体(acceptor,A)，使得应用本发明化合物的OLED器件电子和空穴达到平衡状态，使得器件效率和寿命得到提升。As can be seen from the above table data, the compound of the present invention has high thermal stability, a suitable HOMO level, and is suitable as a light-emitting layer material; meanwhile, the compound of the present invention contains an electron donor (donor, D) and an electron acceptor (acceptor, A), the electrons and holes of the OLED device to which the compound of the present invention is applied are brought to an equilibrium state, so that device efficiency and lifetime are improved.
以下通过实施例19-27和比较例1-3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。实施例20-27与实施例19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，所不同的是器件中发光层的主体材料发生了改变。实施例19-27与比较例1-3相比，比较例1-3所述器件的发光层材料采用的是现有常用原料，而实施例19-27的器件发光层主体材料采用的是本发明化合物。各实施例所得器件的结构组成如表2所示。各器件的性能测试结果见表3。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 19-27 and Comparative Examples 1-3. Embodiments 20-27 Compared with Example 19, the fabrication process of the device is completely the same, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also consistent, except that the light-emitting layer in the device is different. The subject material has changed. Examples 19-27 Compared with Comparative Examples 1-3, the light-emitting layer materials of the devices of Comparative Examples 1-3 were conventional materials, and the device light-emitting layer body materials of Examples 19-27 were Inventive compound. The structural composition of the device obtained in each example is shown in Table 2. The performance test results of each device are shown in Table 3.
实施例19Example 19
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C22和GD-19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)/阴极电极层8(Al)。各化合物的分子结构式如下：Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO 3 , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compounds C22 and GD-19 according to 100 : 5 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al). The molecular structure of each compound is as follows:
Figure PCTCN2017097614-appb-000044
Figure PCTCN2017097614-appb-000044
Figure PCTCN2017097614-appb-000045
Figure PCTCN2017097614-appb-000045
具体制备过程如下：The specific preparation process is as follows:
透明基板层1采用透明材料，如玻璃；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、干燥后再进行紫外线-臭氧洗涤以清除透明ITO表面的有机残留物。The transparent substrate layer 1 is made of a transparent material such as glass; the ITO anode layer 2 (having a film thickness of 150 nm) is washed, that is, sequentially washed with alkali, washed with pure water, dried, and then subjected to ultraviolet-ozone washing to remove the organic surface of the transparent ITO. the remains.
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。On the ITO anode layer 2 after the above washing, molybdenum trioxide MoO 3 having a thickness of 10 nm was deposited as a hole injecting layer 3 by a vacuum vapor deposition apparatus. Next, a TASC having a thickness of 80 nm was evaporated as the hole transport layer 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C22作为主体材料，GD-19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。After the vapor deposition of the hole transporting material is completed, the light emitting layer 5 of the OLED light emitting device is formed, and the structure thereof comprises the material compound C22 used as the host material of the OLED light emitting layer 5, and GD-19 is used as a doping material, and the doping ratio of the doping material is The film thickness of the light-emitting layer was 5% by weight.
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。After the above-mentioned light-emitting layer 5, the vacuum evaporation electron-transporting layer material was continued to be TPBI, and the vacuum-deposited film thickness of the material was 40 nm, and this layer was the electron-transport layer 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。On 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.
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。On the electron injecting 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.
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，测量器件的发光效率，发光光谱以及器件的电流-电压特性。 After the OLED light-emitting device is completed as described above, the anode and the cathode are connected by a known driving circuit, and the luminous efficiency, the luminescence spectrum, and the current-voltage characteristics of the device are measured.
实施例20Example 20
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C29和Ir(PPy)3按照100:10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)/阴极电极层8(Al)。 Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO 3 , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compound C29 and Ir (PPy) 3 The mixture was mixed in a weight ratio of 100:10, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).
实施例21Example 21
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C30和Ir(PPy)3按照100:10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)/阴极电极层8(Al)。 Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO 3 , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compound C30 and Ir (PPy) 3 The mixture was mixed in a weight ratio of 100:10, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).
实施例22Example 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C55和GD-PACTZ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)/阴极电极层8(Al)。 Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO 3 , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compound C55 and GD-PACTZ according to 100 : 5 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).
实施例23Example 23
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C70和GD-PACTZ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)/阴极电极层8(Al)。 Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO 3 , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compound C70 and GD-PACTZ according to 100 : 5 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).
实施例24Example 24
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C108、GH-204和Ir(PPy)3按照70:30:10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)/阴极电极层8(Al)。 Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO 3 , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compounds C108, GH-204 and Ir (PPy) 3 was blended in a weight ratio of 70:30:10, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).
实施例25Example 25
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C117、GH-204和GD-PACTZ按照70:30:5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)/阴极电极层8(Al)。 Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO 3 , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compounds C117, GH-204 and GD - PACTZ was blended in a weight ratio of 70:30:5, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).
比较例1Comparative example 1
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(CBP和GD-19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)/阴极电极层8(Al)。The transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO 3, thickness 10 nm) / hole transport layer 4 (TAPC, 80nm thickness) / light-emitting layer 5 (CBP 100 and GD-19 in accordance with: 5 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).
比较例2Comparative example 2
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(CBP和Ir(PPy)3按照100:10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)/阴极电极层8(Al)。 Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO 3 , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (CBP and Ir (PPy) 3 according to 100:10 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).
比较例3Comparative example 3
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(CBP和GD-PACTZ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)/阴极电极层8(Al)。 Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO 3 , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (CBP and GD-PACTZ according to 100: 5 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).
所制作的OLED发光器件的测试结果见表3。The test results of the fabricated OLED light-emitting device are shown in Table 3.
表2Table 2
Figure PCTCN2017097614-appb-000046
Figure PCTCN2017097614-appb-000046
Figure PCTCN2017097614-appb-000047
Figure PCTCN2017097614-appb-000047
表3table 3
Figure PCTCN2017097614-appb-000048
Figure PCTCN2017097614-appb-000048
从表3的结果可以看出本发明所述化合物作为发光层主体材料可应用与OLED发光器件制作，并且与比较例1-3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。It can be seen from the results of Table 3 that the compound of the present invention can be used as a host material of the light-emitting layer to be fabricated with an OLED light-emitting device, and compared with Comparative Example 1-3, both the efficiency and the lifetime are larger than those of the known OLED material. The improvement, especially the drive life of the device, has been greatly improved.
从以上数据应用来看，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。From the above data application, the compound of the invention has good application effect as an luminescent layer material in an OLED light-emitting device, and has a good industrialization prospect.
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。 While the invention has been disclosed by the embodiments and the preferred embodiments, it is understood that the invention is not limited to the disclosed embodiments. Instead, it will be apparent to those skilled in the art that the various modifications and similar arrangements are contemplated. Therefore, the scope of the appended claims should be accorded

Claims (9)

  1. 一种以氧杂蒽酮为核心的化合物，其特征在于所述化合物的结构如通式(1)所示：A compound having a xanthone as a core, characterized in that the structure of the compound is as shown in the formula (1):
    Figure PCTCN2017097614-appb-100001
    三联苯基、萘基、蒽基或菲基；m、n分别独立的选取1或2；
    Figure PCTCN2017097614-appb-100001
    Terphenyl, naphthyl, anthracenyl or phenanthryl; m, n are independently selected 1 or 2;
    通式(1)中
    Figure PCTCN2017097614-appb-100002
    表示(Ar)m连接在通式(1)两侧苯环上的任意碳原子上；    In the general formula (1)
    Figure PCTCN2017097614-appb-100002
    Indicates that (Ar) m is attached to any carbon atom on the benzene ring on both sides of the formula (1);
    R采用通式(2)、通式(3)、通式(4)或通式(5)表示：R is represented by the general formula (2), the general formula (3), the general formula (4) or the general formula (5):
    Figure PCTCN2017097614-appb-100003
    Figure PCTCN2017097614-appb-100003
    其中，among them,
    X1、Y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；X 1 , Y are 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 substituted tertiary amine group. a kind
    R1选取通式(6)所示结构，R2选取通式(7)所示结构：R 1 is selected from the structure represented by the general formula (6), and R 2 is selected from the structure represented by the general formula (7):
    Figure PCTCN2017097614-appb-100004
    Figure PCTCN2017097614-appb-100004
    a为
    Figure PCTCN2017097614-appb-100005
    X2、X3分别表示为氧原子、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通过CL1-CL2键、CL2-CL3键、CL3-CL4键、CL4-CL5键、CL‘1-CL’2键、CL‘2-CL’3键、CL‘3-CL’4键或CL‘4-CL’5键连接在通式(2)或通式(4)上；    a is
    Figure PCTCN2017097614-appb-100005
    X 2 and X 3 are each 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 substituted tertiary group. One of the amine groups; a through the C L1 -C L2 bond, the C L2 -C L3 bond, the C L3 -C L4 bond, the C L4 -C L5 bond, the C L'1 -C L'2 bond, C L a '2 -C L'3 bond, a C L'3 -C L'4 bond or a C L'4 -C L'5 bond is attached to the formula (2) or the formula (4);
    Ar2、Ar3分别独立的表示为苯基、C1-10直链或支链烷基取代的苯基、二联苯基、三联苯基、或萘基中的一种； Ar 2 and Ar 3 are each independently represented by a phenyl group, a C 1-10 linear or branched alkyl substituted phenyl group, a diphenyl group, a terphenyl group, or a naphthyl group;
    R3、R4分别独立的表示为碳原子为1-10的烷基、取代或者未取代的碳原子为1-50的芳基、芳基或烷基取代的碳原子为1-50的胺基、取代或者未取代的碳原子为1-50的杂芳基。R 3 and R 4 are each independently represented by an alkyl group having 1 to 10 carbon atoms, an substituted or unsubstituted aryl group having 1 to 50 carbon atoms, an aryl group or an alkyl group having 1 to 50 carbon atoms. The substituted, unsubstituted or unsubstituted carbon atom is a heteroaryl group of 1 to 50.
  2. 根据权利要求1所述的化合物，其特征在于所述R3、R4分别独立的选取碳原子为1-10的烷基、苯基、C1-10直链或支链烷基取代的苯基、二联苯基、三联苯基、萘基、通式(8)、通式(9)、通式(10)或通式(11)所示结构；The compound according to claim 1, wherein said R 3 and R 4 are each independently selected from the group consisting of an alkyl group having a carbon atom of 1 to 10, a phenyl group, a C 1-10 linear or branched alkyl group substituted benzene. a structure represented by a group, a diphenyl group, a terphenyl group, a naphthyl group, a formula (8), a formula (9), a formula (10) or a formula (11);
    Figure PCTCN2017097614-appb-100006
    Figure PCTCN2017097614-appb-100006
    其中，Ar4、Ar5、Ar6分别独立的表示苯基、C1-10直链或支链烷基取代的苯基、二联苯基、三联苯基、萘基、C1-10直链或支链烷基取代的苯并呋喃基、C1-10直链或支链烷基取代的苯并噻吩基、C1-10直链或支链烷基取代的芴基、C1-10直链或支链烷基取代的咔唑基中的一种；Wherein, Ar 4 , Ar 5 and Ar 6 each independently represent a phenyl group, a C 1-10 linear or branched alkyl substituted phenyl group, a diphenyl group, a terphenyl group, a naphthyl group, and a C 1-10 straight A chain or branched alkyl substituted benzofuranyl group, a C 1-10 straight or branched alkyl substituted benzothienyl group, a C 1-10 straight or branched alkyl substituted fluorenyl group, C 1- One of 10 linear or branched alkyl substituted oxazolyl groups;
    R5、R6分别独立的选取氢、碳原子为1-10的烷基、或碳原子为4-20的芳香基；R 5 and R 6 are each independently selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 4 to 20 carbon atoms;
    X4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。X 4 represents an oxygen atom, a sulfur atom, a selenium atom, C 1-10 straight-chain or branched-chain alkyl-substituted alkylene, substituted alkylaryl, substituted alkyl or aryl group in the tertiary amine One.
  3. 根据权利要求1所述的化合物，其特征在于所述Ar表示为
    Figure PCTCN2017097614-appb-100007
    时，所述化合物的结构通式表示为：    The compound according to claim 1, wherein said Ar is represented by
    Figure PCTCN2017097614-appb-100007
    The structural formula of the compound is expressed as:
    Figure PCTCN2017097614-appb-100008
    Figure PCTCN2017097614-appb-100008
    Figure PCTCN2017097614-appb-100009
    Figure PCTCN2017097614-appb-100009
    中的任一种。Any of them.
  4. 根据权利要求1所述的化合物，其特征在于所述Ar表示为-R时，所述化合物的结构通式表示为：The compound according to claim 1, wherein when said Ar is represented by -R, the structural formula of said compound is expressed as:
    Figure PCTCN2017097614-appb-100010
    Figure PCTCN2017097614-appb-100010
    中的任一种。Any of them.
  5. 根据权利要求1所述的化合物，其特征在于所述通式(1)中R为：The compound according to claim 1, wherein R in the formula (1) is:
    Figure PCTCN2017097614-appb-100011
    Figure PCTCN2017097614-appb-100011
    Figure PCTCN2017097614-appb-100012
    Figure PCTCN2017097614-appb-100012
    Figure PCTCN2017097614-appb-100013
    Figure PCTCN2017097614-appb-100013
    Figure PCTCN2017097614-appb-100014
    Figure PCTCN2017097614-appb-100014
    Figure PCTCN2017097614-appb-100015
    Figure PCTCN2017097614-appb-100015
    中的任一种。Any of them.
  6. 根据权利要求1所述的化合物，其特征在于所述基于氧杂蒽酮的化合物的具体结构为： The compound according to claim 1, characterized in that the specific structure of the xanthone-based compound is:
    Figure PCTCN2017097614-appb-100016
    Figure PCTCN2017097614-appb-100016
    Figure PCTCN2017097614-appb-100017
    Figure PCTCN2017097614-appb-100017
    Figure PCTCN2017097614-appb-100018
    Figure PCTCN2017097614-appb-100018
    Figure PCTCN2017097614-appb-100019
    Figure PCTCN2017097614-appb-100019
    Figure PCTCN2017097614-appb-100020
    Figure PCTCN2017097614-appb-100020
    Figure PCTCN2017097614-appb-100021
    Figure PCTCN2017097614-appb-100021
    Figure PCTCN2017097614-appb-100022
    Figure PCTCN2017097614-appb-100022
    Figure PCTCN2017097614-appb-100023
    Figure PCTCN2017097614-appb-100024
    Figure PCTCN2017097614-appb-100023
    Figure PCTCN2017097614-appb-100024
    C121中的任一种。Any of C121.
  7. 一种包含权利要求1～6任一项所述化合物的发光器件，其特征在于所述化合物作为发光层材料，用于制作有机电致发光器件。A light-emitting device comprising the compound according to any one of claims 1 to 6, characterized in that the compound is used as a light-emitting layer material for producing an organic electroluminescence device.
  8. 根据权利要求7所述的发光器件，其特征在于所述化合物作为发光层的主体材料，用于制作有机电致发光器件。The light emitting device according to claim 7, wherein said compound is used as a host material of the light-emitting layer for producing an organic electroluminescence device.
  9. 一种制备权利要求1～6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：A process for the preparation of a compound according to any one of claims 1 to 6, characterized in that the reaction equation which occurs during the preparation is:
    Figure PCTCN2017097614-appb-100025
    Figure PCTCN2017097614-appb-100025
    式1反应过程如下：称取氧杂蒽酮为核心的溴代化合物和R-H，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、过滤反应溶液，滤液旋蒸，过硅胶柱，得到目标产物；The reaction process of Formula 1 is as follows: weigh the brominated compound with the xanthone as the core and RH, and dissolve it with toluene; then add Pd 2 (dba) 3 , tri-tert-butylphosphine, sodium t-butoxide; under an inert atmosphere, The mixed solution of the above reactants is reacted at a reaction temperature of 95 to 110 ° C for 10 to 24 hours, and the reaction solution is cooled and filtered, and the filtrate is subjected to rotary distillation to pass through a silica gel column to obtain a target product;
    所述氧杂蒽酮为核心的溴化物与R-H的摩尔比为1:1.0～4.0；Pd2(dba)3与氧杂蒽酮为核心的溴化物的摩尔比为0.006～0.02:1，三叔丁基膦与氧杂蒽酮为核心的溴化物的摩尔比为0.006～0.02:1，叔丁醇钠与氧杂蒽酮为核心的溴化物的摩尔比为1.0～4.0:1； The molar ratio of the bromide to the RH of the xanthone is 1:1.0-4.0; the molar ratio of the bromide of the Pd 2 (dba) 3 to the xanthone is 0.006-0.02:1, three The molar ratio of tert-butylphosphine to xanthone as the core bromide is 0.006 to 0.02:1, and the molar ratio of sodium t-butoxide to xanthone as the core bromide is 1.0 to 4.0:1;
    式2反应过程如下：称取氧杂蒽酮为核心的溴代化合物和Ar-B(OH)2，用甲苯溶解；再加入Pd(PPh3)4、碳酸钠；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、过滤反应溶液，滤液旋蒸，过硅胶柱，得到目标产物；The reaction process of Formula 2 is as follows: weigh the brominated compound with the xanthone as the core and Ar-B(OH) 2 , and dissolve it with toluene; then add Pd(PPh 3 ) 4 and sodium carbonate; under the inert atmosphere, the above The mixed solution of the reactants is reacted at a reaction temperature of 95 to 110 ° C for 10 to 24 hours, and the reaction solution is cooled and filtered, and the filtrate is rotary-screwed and passed through a silica gel column to obtain a target product;
    所述氧杂蒽酮为核心的溴化物与Ar-B(OH)2的摩尔比为1:1.0～4.0；Pd(PPh3)4与氧杂蒽酮为核心的溴化物的摩尔比为0.006～0.02:1，碳酸钠与氧杂蒽酮为核心的溴化物的摩尔比为1.0～4.0:1。 The molar ratio of the bromide to the Ar-B(OH) 2 of the xanthone is 1:1.0-4.0; the molar ratio of the bromide of the Pd(PPh 3 ) 4 to the xanthone is 0.006. ～0.02:1, the molar ratio of sodium carbonate to xanthone as the core bromide is 1.0 to 4.0:1.
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