WO2020098138A1 - 一种深蓝光热活化延迟荧光材料及其应用 - Google Patents

一种深蓝光热活化延迟荧光材料及其应用 Download PDF

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WO2020098138A1
WO2020098138A1 PCT/CN2019/071069 CN2019071069W WO2020098138A1 WO 2020098138 A1 WO2020098138 A1 WO 2020098138A1 CN 2019071069 W CN2019071069 W CN 2019071069W WO 2020098138 A1 WO2020098138 A1 WO 2020098138A1
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thermally activated
activated delayed
fluorescent material
delayed fluorescent
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Definitions

  • the invention relates to the field of materials that can be used for flat display devices, in particular, a deep blue light thermally activated delayed fluorescent material and a preparation method thereof.
  • organic light-emitting diodes do not require a backlight source for their active light emission, high luminous efficiency, large viewing angle, fast response speed, large temperature adaptation range, relatively simple production and processing technology, The advantages of low driving voltage, small energy consumption, lighter and thinner, flexible display and huge application prospects have attracted the attention of many researchers.
  • OLED organic light-emitting diodes
  • the luminescent guest material that plays a leading role is very important.
  • the luminescent guest materials used in early OLEDs were fluorescent materials. Because the ratio of singlet and triplet excitons in OLED is 1: 3, the theoretical internal quantum efficiency (IQE) of OLED based on fluorescent materials can only reach 25% , which greatly limits the application of fluorescent electroluminescent devices.
  • Heavy metal complex phosphorescent materials can achieve 100% IQE by utilizing singlet and triplet excitons simultaneously due to the spin-orbit coupling of heavy atoms.
  • the commonly used heavy metals are precious metals such as Ir and Pt, and the phosphorescent luminescent materials of the heavy metal complexes have yet to be broken through in terms of blue light materials.
  • TADF organic thermally activated delayed fluorescence
  • TADF materials For TADF materials, fast reverse intersystem crossing constant (kRISC) and high photoluminescence quantum yield (PLQY) are necessary conditions for the preparation of high-efficiency OLEDs. At present, TADF materials with the above conditions are still relatively scarce compared to the heavy metal Ir complexes. Especially in the field of deep blue light where phosphorescent heavy metal materials need to be broken through, TADF materials are rare.
  • kRISC fast reverse intersystem crossing constant
  • PLQY photoluminescence quantum yield
  • One aspect of the present invention is to provide a deep blue thermally activated delayed fluorescence (Thermally Activated Delayed Fluorescence, TADF) material, which constitutes a compound molecule with an ultrafast reverse intersystem crossing rate, and when it is doped In the light-emitting layer of the electroluminescent device, the blue-light fluorescent and phosphorescent electroluminescent device using it as a host material can achieve very high efficiency.
  • TADF Thermally activated delayed fluorescence
  • a deep blue thermally activated delayed fluorescent material the molecular structure of which constitutes Compound 1 is as follows:
  • the intermediate is synthesized from the raw material 4-bromophosphorone, wherein the molecular structure of the 4-bromophosphorone is as follows:
  • the intermediate is synthesized using the following synthetic route:
  • 9,10-dihydro-9,9-dimethylacridine is derived as 9,10-dihydro-9,9-diphenylacridine, combined with the Intermediate, so that the compound 1 involved in the present invention is derived into compound 2, and the molecular structure of the compound 2 is as follows:
  • the present invention has disclosed three compounds. Although the molecular structures of these three compounds are slightly different, they are all based on a creative concept, and the basic raw materials and intermediates involved are also consistent. The raw materials of acridine used in the synthesis are different, but they are also similar derivatives. Therefore, the three different compounds involved in the present invention belong to the same inventive concept and have unity.
  • Another aspect of the present invention provides a method for preparing the compound 1 according to the present invention, which includes the following steps:
  • Another aspect of the present invention provides a method for preparing the compound 2 according to the present invention, which includes the following steps:
  • reaction solution was poured into ice water, and extracted with dichloromethane 3 to 5 times.
  • the organic phases were combined, spinned into silica gel, and separated and purified by column chromatography to obtain the compound 2 as a blue-white powder.
  • Another aspect of the present invention provides a method for preparing the compound 3 according to the present invention, which includes the following steps:
  • an electroluminescent device which includes a light emitting layer.
  • the material of the light-emitting layer includes at least one of Compound 1, Compound 2, or Compound 3 involved in the present invention.
  • the invention achieves the purpose of reducing the difference between the lowest single and triple energy levels of target molecules and the high energy level by screening different electron donor units, adjusting the torsion angle and charge transfer characteristics between the electron donor and the electron acceptor
  • the molecules of the target compound 1, compound 2 and compound 3 involved in the present invention have an ultra-fast reverse intersystem crossing rate, and when they are doped in the light emitting layer of the applied device as their host, so that they are used as Both the blue fluorescence of the host material and the phosphorescent electroluminescent device can achieve very high efficiency.
  • HOMO highest electron occupied orbit
  • Fig. 2 is the distribution diagram of the lowest electron unoccupied orbit (LUMO) of the deep-blue thermally activated delayed fluorescent material shown in Fig. 1;
  • LUMO lowest electron unoccupied orbit
  • FIG. 3 is a distribution diagram of the highest electron-occupied orbit (HOMO) obtained by theoretical calculation when the compound structure of the deep blue light thermally activated delayed fluorescent material provided by another embodiment of the present invention is the compound 2. ;
  • HOMO highest electron-occupied orbit
  • FIG. 4 is the distribution diagram of the lowest electron unoccupied orbit (LUMO) of the deep-blue thermally activated delayed fluorescent material shown in FIG. 3;
  • LUMO lowest electron unoccupied orbit
  • HOMO 5 is a distribution diagram of the highest electron-occupied orbit (HOMO) obtained by theoretical calculation when the compound structure of the deep blue light thermally activated delayed fluorescent material provided by another embodiment of the present invention is the compound 3; ;
  • FIG. 6 is a distribution diagram of the lowest electron unoccupied orbit (LUMO) of the deep-blue thermally activated delayed fluorescent material shown in FIG. 5 after theoretical calculation;
  • LUMO lowest electron unoccupied orbit
  • FIG. 8 is a transient photoluminescence spectrum of each compound in three embodiments of the present invention in a toluene solution at room temperature.
  • One embodiment of the present invention provides a deep blue thermally activated delayed fluorescent material, and the structural formula of the compound is as follows:
  • the compound 1 also derives the compound 2 and the compound 3, and their structural formulas are as follows:
  • FIGS. 1 to 6 show that the three compounds involved in the present invention are calculated by theoretical calculation of the distribution of the highest electron occupied orbit (HOMO) and the lowest electron not occupied Distribution of the orbit (LUMO).
  • HOMO highest electron occupied orbit
  • LUMO lowest electron not occupied Distribution of the orbit
  • the lowest singlet state (S1) and lowest triplet state energy level (T1) of the compound 1, compound 2 and compound 3 are as shown in the following table:
  • FIG. 7 illustrates the photoluminescence spectra of three different compounds in the three embodiments of the present invention in toluene solution at room temperature.
  • FIG. 8 illustrates the transient photoluminescence spectra of three different compounds in the three embodiments of the present invention in toluene solution at room temperature.
  • intermediate synthesis stage It is divided into two stages: intermediate synthesis stage and compound 1 synthesis stage. among them
  • reaction solution was poured into 50 mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spinned into silica gel, and column chromatography (dichloromethane: n-hexane, v: v, 2: 1) was separated and purified.
  • the target compound 1 as a blue-white powder was 1.8 g, and the yield was 58%.
  • the compound 2 and the compound 3 are also divided into two stages: intermediate synthesis stage and compound synthesis stage.
  • intermediate synthesis stage The structure of the raw materials and the final intermediate involved in the intermediate synthesis stage is the same as the intermediate of the compound 1. Therefore, in order to avoid unnecessary repetition, only the synthesis stage of the compound 2 and the compound 3 will be described below.
  • reaction solution was poured into 50 mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spinned into silica gel, and column chromatography (dichloromethane: n-hexane, v: v, 2: 1) was separated and purified.
  • the target compound 2 as a blue-white powder was 2.4 g, and the yield was 76%.
  • the synthetic route of the compound 3 is as follows:
  • reaction solution was poured into 50 mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spinned into silica gel, and column chromatography (dichloromethane: n-hexane, v: v, 3: 1) was separated and purified.
  • the target compound 3 as a blue-white powder was 2.1 g, and the yield was 65%.
  • the deep blue thermally activated delayed fluorescent material according to the present invention can be used to form a light emitting layer in an electroluminescent device.
  • the electroluminescent device includes a glass and conductive glass (ITO) substrate layer, a hole transport and injection layer (poly 3,4-ethylenedioxythiophene: polystyrene sulfonate, PEDOT: PSS), luminescent layer 3 (the host material of the present invention with delayed fluorescence and blue phosphorescent guest Firpic), electron transport layer (1,3,5-tris (3- (3-pyridyl) phenyl) benzene Tm3PyPB) And cathode layer 5 lithium fluoride / aluminum)
  • ITO glass and conductive glass
  • PEDOT polystyrene sulfonate
  • luminescent layer 3 the host material of the present invention with delayed fluorescence and blue phosphorescent guest Firpic
  • electron transport layer (1,3,5-tris (3- (3-pyridyl) phenyl) benzene Tm3PyPB)
  • the electroluminescent device may be spin coating on the washed conductive glass (ITO) substrate in sequence: PESOT: PSS, thermally activated delayed fluorescent host + phosphorescent guest, and then in Under high vacuum conditions, TmPyPB, 1 nm LiF and 100 nm Al were deposited in sequence.
  • ITO washed conductive glass
  • electroluminescent devices combining the compound 1, the compound 2 and the compound 3 according to the present invention respectively, the specific device structure is as follows:
  • ITO / PEDOT PSS (50nm) / Compound 2: Firpic (5% 40nm) / TmPyPB (40nm) / LiF (1nm) / Al (100nm)
  • ITO / PEDOT PSS (50nm) / Compound 3: Firpic (5% 40nm) / TmPyPB (40nm) / LiF (1nm) / Al (100nm)
  • the performance measurement of the above electroluminescent devices is carried out, wherein the current-luminance-voltage characteristics of the device are completed by a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000, Currentmeter) with a corrected silicon photodiode
  • the electroluminescence spectrum is measured by SPEX CCD3000 spectrometer of French company JY. All measurements are done in the room temperature atmosphere.
  • the invention obtains a series of deep blue thermally activated delayed fluorescent materials with remarkable TADF characteristics through the combination of different functional groups. At the same time, the design of the synthetic route is reasonable and the synthesis efficiency of the target material is high.
  • the organic electroluminescent device prepared by using the deep blue thermally activated delayed fluorescent material according to the present invention has high luminous efficiency and excellent device effect.

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Abstract

提供一种深蓝光热活化延迟荧(Thermally Activated Delayed Fluorescence,TADF)材料，其构成化合物分子具有超快的反向系间窜越速率，并且当其作为主体掺杂在电致发光器件中的发光层中时，使得以其作为主体材料的蓝光荧光以及磷光的电致发光器件都能取得非常高的效率。

Description

一种深蓝光热活化延迟荧光材料及其应用 技术领域
本发明涉及可用于平面显示器件的材料领域，尤其是，其中的一种深蓝光热活化延迟荧光材料及其制备方法。
背景技术
已知，有机电致发光二极管(organic light-emitting diodes，OLEDs)以其主动发光不需要背光源、发光效率高、可视角度大、响应速度快、温度适应范围大、生产加工工艺相对简单、驱动电压低，能耗小，更轻更薄，柔性显示等优点以及巨大的应用前景，吸引了众多研究者的关注。而在OLED中，起主导作用的发光客体材料至关重要。
早期的OLED使用的发光客体材料为荧光材料，由于在OLED中单重态和三重态的激子比例为1:3，因此基于荧光材料的OLED的理论内量子效率(IQE)只能达到25％，极大的限制了荧光电致发光器件的应用。重金属配合物磷光材料由于重原子的自旋轨道耦合作用，使得它能够同时利用单重态和三重态激子而实现100％的IQE。然而，通常使用的重金属都是Ir、Pt等贵重金属，并且重金属配合物磷光发光材料在蓝光材料方面尚有待突破。
纯有机热活化延迟荧光(TADF)材料，通过巧妙的分子设计，使得分子具有较小的最低单三重能级差(ΔEST)，这样三重态激子可以通过反向系间窜越(RISC)回到单重态，再通过辐射跃迁至基态而发光，从而能够同时利用单、三重态激子，也可以实现100％的IQE。
对于TADF材料，快速的反向系间窜越常数(kRISC)以及高的光致发光量子产率(PLQY)是制备高效率OLED的必要条件。目前，具备上述条件的TADF材料相对于重金属Ir配合物而言还是比较匮乏，尤其是在磷光重金属材料有待突破的深蓝光领域，TADF材料方面更是寥寥无几。
因此，设计合成新型的深蓝光TADF聚合物对于开拓TADF材料的广泛应用，具有十分重要的意义。
技术问题
本发明的的一个方面在于提供一种深蓝光热活化延迟荧光(Thermally Activated Delayed Fluorescence,TADF)材料，其构成化合物分子具有超快的反向系间窜越速率，并且当其作为主体掺杂在电致发光器件的发光层中时，使得以其作为主体材料的蓝光荧光以及磷光的电致发光器件都能取得非常高的效率。
技术解决方案
其中本发明采用的技术方案如下：
一种深蓝光热活化延迟荧光材料，其构成化合物1的分子结构式如下：
Figure PCTCN2019071069-appb-000001
进一步的，在不同实施方式中，其中所述化合物1是通过中间体结合9,10-二氢-9,9-二 甲基吖啶合成出的，其中所述中间体的分子结构式如下：
Figure PCTCN2019071069-appb-000002
进一步的，在不同实施方式中，其中所述化合物1是采用以下合成路线合成出的：
Figure PCTCN2019071069-appb-000003
进一步的，在不同实施方式中，其中所述中间体是以原料4-溴磷酮合成出的，其中所述4-溴磷酮的分子结构式如下：
Figure PCTCN2019071069-appb-000004
进一步的，在不同实施方式中，其中所述中间体是采用以下合成路线合成出的：
Figure PCTCN2019071069-appb-000005
进一步的，在不同实施方式中，其中所述9,10-二氢-9,9-二甲基吖啶衍生为9,10-二氢-9,9-二苯基吖啶，结合所述中间体，使得本发明涉及的所述化合物1衍生为化合物2，所述化合物2的分子结构式如下：
Figure PCTCN2019071069-appb-000006
进一步的，在不同实施方式中，其中所述化合物2是采用以下合成路线合成出的：
Figure PCTCN2019071069-appb-000007
进一步的，在不同实施方式中，其中所述9,10-二氢-9,9-二甲基吖啶衍生为9,10-二氢-9,9-二苯基硅代吖啶，结合所述中间体，使得本发明涉及的所述化合物1衍生为化合物3，所述化合物3的分子结构式如下：
Figure PCTCN2019071069-appb-000008
进一步的，在不同实施方式中，其中所述化合物3是采用以下合成路线合成出的：
Figure PCTCN2019071069-appb-000009
进一步的，以上本发明揭示了三种化合物，虽然这三种化合物的分子式结构有稍许不同，但其均是根据一个创作构思做出的，且涉及的基础原料和中间体也是一致的，虽然后续合成中采用的吖啶原料有所不同，但也是相近的衍生物。因此，本发明涉及的这三种不同化合物之间属于同一个发明构思，具有单一性。
进一步的，本发明的又一方面提供了一种本发明涉及的所述化合物1的制备方法，其包括以下步骤：
向反应瓶中加入4-溴磷酮和二氯甲烷(DCM)以及(25～35)％的过氧化氢水溶液，然后在在室温下反应20～30小时；
将反应液倒入冰水中，抽滤得灰白色固体，用二氯甲烷溶解，旋成硅胶，柱层析分离纯化，得白色粉末状中间体；
向反应瓶中加入所述中间体、9,10-二氢-9,9-二甲基吖啶、醋酸钯和三叔丁基膦四氟硼酸盐，然后在手套箱中加入NaOt-Bu，在惰性气体(例如，氩气)氛围下打入已除水除氧的甲苯，在110～130℃反应40～60小时；
冷却至室温，将反应液倒入冰水中，二氯甲烷萃取3～5次，合并有机相，旋成硅胶，柱层析分离纯化，得蓝白色粉末状所述化合物1。
进一步的，本发明的又一方面提供了一种本发明涉及的所述化合物2的制备方法，其包括以下步骤：
向反应瓶中加入4-溴磷酮和二氯甲烷(DCM)以及(25～35)％的过氧化氢水溶液，然后在在室温下反应20～30小时；
将反应液倒入冰水中，抽滤得灰白色固体，用二氯甲烷溶解，旋成硅胶，柱层析分离纯化，得白色粉末状中间体；
向反应瓶中加入所述中间体、9,10-二氢-9,9-二苯基吖啶、醋酸钯和三叔丁基膦四氟硼酸 盐，然后在手套箱中加入NaOt-Bu，在惰性气体(例如，氩气)氛围下打入已除水除氧的甲苯，在110～130℃反应40～60小时；
冷却至室温，将反应液倒入冰水中，二氯甲烷萃取3～5次，合并有机相，旋成硅胶，柱层析分离纯化，得蓝白色粉末状所述化合物2。
进一步的，本发明的又一方面提供了一种本发明涉及的所述化合物3的制备方法，其包括以下步骤：
向反应瓶中加入4-溴磷酮和二氯甲烷(DCM)以及(25～35)％的过氧化氢水溶液，然后在在室温下反应20～30小时；
将反应液倒入冰水中，抽滤得灰白色固体，用二氯甲烷溶解，旋成硅胶，柱层析分离纯化，得白色粉末状中间体；
向反应瓶中加入所述中间体、9,10-二氢-9,9-二苯基硅代吖啶、醋酸钯和三叔丁基膦四氟硼酸盐，然后在手套箱中加入NaOt-Bu，在惰性气体(例如，氩气)氛围下打入已除水除氧的甲苯，在110～130℃反应40～60小时；
冷却至室温，将反应液倒入冰水中，二氯甲烷萃取3～5次，合并有机相，旋成硅胶，柱层析分离纯化，得蓝白色粉末状所述化合物3。
进一步的，本发明的又一方面提供了一种电致发光器件，其包括发光层。其中所述发光层的材料包括本发明涉及的所述化合物1、化合物2或是化合物3中的至少一种。
有益效果
本发明通过筛选不同的电子给体单元，调节电子给体与电子受体之间的扭转角以及电荷转移(Charge Transfer)特性，达到减小目标分子最低单三重能级差以及高能级的目的，从而使得本发明涉及的所述目标化合物1、化合物2以及化合物3的分子具有超快的反向系间窜越速率，并且当以其作为主体掺杂在应用器件的发光层中，使得以其作为主体材料的蓝光荧光以及磷光的电致发光器件都能取得非常高的效率。
附图说明
图1是本发明涉及的一个实施方式提供的一种深蓝光热活化延迟荧光材料，其分子结构采用所述化合物1时，经过理论计算得出的其最高电子占据轨道(HOMO)的分布图；
图2是图1所示的深蓝光热活化延迟荧光材料，经过理论计算得出的其最低电子未占据轨道(LUMO)的分布图；
图3是本发明涉及的又一个实施方式提供的一种深蓝光热活化延迟荧光材料，其分子结构采用所述化合物2时，经过理论计算得出的其最高电子占据轨道(HOMO)的分布图；
图4是图3所示的深蓝光热活化延迟荧光材料，经过理论计算得出的其最低电子未占据轨道(LUMO)的分布图；
图5是本发明涉及的又一个实施方式提供的一种深蓝光热活化延迟荧光材料，其分子结构采用所述化合物3时，经过理论计算得出的其最高电子占据轨道(HOMO)的分布图；
图6是图5所示的深蓝光热活化延迟荧光材料，经过理论计算得出的其最低电子未占据轨道(LUMO)的分布图；
图7是本发明涉及的3个实施方式中的各化合物，在室温下、甲苯溶液中的光致发光光谱；
图8是本发明涉及的3个实施方式中的各化合物，在室温下、甲苯溶液中的瞬态光致发光光谱。
本发明的实施方式
以下将结合附图和实施例，对本发明涉及的一种深蓝光热活化延迟荧光材料及其应用的技术方案作进一步的详细描述。
本发明的一个实施方式提供了一种深蓝光热活化延迟荧光材料，其构成化合物的结构式如下：
Figure PCTCN2019071069-appb-000010
进一步的，通过不同原料衍生官能团的搭配，所述化合物1还衍生出化合物2和化合物3，其结构式分别如下：
Figure PCTCN2019071069-appb-000011
进一步的，其中请参阅图1～6所示，其图示了，本发明涉及的这三种化合物，经过理论计算得出的其最高电子占据轨道(HOMO)的分布，以及其最低电子未占据轨道(LUMO)的分布。
进一步的，所述化合物1、化合物2和化合物3，其最低单重态(S1)和最低三重态能级(T1)，电化学能级如下表所示：
Figure PCTCN2019071069-appb-000012
请参阅图7所示，其图示了本发明涉及的三个实施方式中的三个不同化合物，在室温下、甲苯溶液中的光致发光光谱。
请参阅图8所示，其图示了本发明涉及的三个实施方式中的三个不同化合物，在室温下、甲苯溶液中的瞬态光致发光光谱。
以下将结合具体制备方法，对所述各化合物进行进一步的详细说明。
其中所述化合物1的合成路线如下所示：
Figure PCTCN2019071069-appb-000013
其具体分为两个阶段：中间体合成阶段和化合物1合成阶段。其中
中间体合成阶段：
向100mL二口瓶中加入4-溴磷酮(3.65g，10mmol)，打入60mL二氯甲烷(DCM)，10mL 30％的过氧化氢水溶液，然后在在室温下反应24小时；
将反应液倒入200mL冰水中，抽滤得灰白色固体，用二氯甲烷溶解，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，2:1)分离纯化，得白色粉末状的中间体3.6g，产率94％。(1H NMR(300MHz,CD2Cl2,δ):7.94(d,J＝6.0Hz,2H),7.87(d,J＝6.3Hz,2H),7.77-7.70(m,4H),7.38(d,J＝6.6Hz,2H),7.28(d,J＝6.9Hz,2H).MS(EI)m/z:[M]+calcd for C19H12BrO2P,381.98；found,381.87.Anal.Calcd for C19H12BrO2P:C 59.56,H 3.16；found:C59.31,H 3.07.)
化合物1合成阶段：
向100mL二口瓶中加入中间体1(1.91g，5mmol)，9,10-二氢-9,9-二甲基吖啶(1.14g，6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入NaOt-Bu(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应48小时；
冷却至室温，将反应液倒入50mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，2:1)分离纯化，得蓝白色粉末状目标化合物1为1.8g，产率58％。(1H NMR(300MHz,CD2Cl2,δ):7.94(d,J＝6.0Hz,2H),7.87(d,J＝6.3Hz,2H),7.77-7.70(m,4H),7.38(d,J＝6.6Hz,2H),7.19-7.14(m,8H),6.95(d,J＝6.0Hz,2H),1.69(s,6H).MS(EI)m/z:[M]+calcd for C34H26NO2P,511.17；found,511.09.Anal.Calcd for C34H26NO2P:C 79.83,H 5.12,N 2.74；found:C 79.67,H 5.07,N 2.62.)
其中所述化合物2和化合物3也是分为两个阶段：中间体合成阶段和化合物合成阶段。其中由于中间体合成阶段涉及的原料和最终中间体的结构与所述化合物1的中间体是一致的，因此，为避免不必要的重复，以下只对化合物2和化合物3的合成阶段进行说明。
其中所述化合物2的合成路线如下所示：
Figure PCTCN2019071069-appb-000014
其具体包括以下合成步骤：
向100mL二口瓶中加入中间体1(1.91g，5mmol)，9,10-二氢-9,9-二苯基吖啶(2.00g， 6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入NaOt-Bu(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应48小时；
冷却至室温，将反应液倒入50mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，2:1)分离纯化，得蓝白色粉末状目标化合物2为2.4g，产率76％。(1H NMR(300MHz,CD2Cl2,δ):7.94(d,J＝6.0Hz,2H),7.87(d,J＝6.3Hz,2H),7.77-7.70(m,4H),7.38(d,J＝6.6Hz,2H),7.19-7.00(m,16H),6.95-6.87(m,4H).MS(EI)m/z:[M]+calcd for C44H30NO2P,635.20；found,635.09.Anal.Calcd for C44H30NO2P:C 83.13,H 4.76,N 2.20；found:C 83.00,H 4.66,N 2.12.)
其中所述化合物3的合成路线如下所示：
Figure PCTCN2019071069-appb-000015
其具体包括以下合成步骤：
向100mL二口瓶中加入中间体1(1.91g，5mmol)，9,10-二氢-9,9-二苯基硅代吖啶(2.00g，6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入NaOt-Bu(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应48小时；
冷却至室温，将反应液倒入50mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，3:1)分离纯化，得蓝白色粉末状目标化合物3为2.1g，产率65％。(1H NMR(300MHz,CD2Cl2,δ):7.94(d,J＝6.0Hz,2H),7.87(d,J＝6.3Hz,2H),7.77-7.60(m,12H),7.50-7.38(m,10H),7.26(d,J＝6.9Hz,2H),6.97(d,J＝6.3Hz,2H).MS(EI)m/z:[M]+calcd for C43H30NO2PSi,651.18；found,651.09.Anal.Calcd for C43H30NO2PSi:C 79.24,H 4.64,N 2.15；found:C 79.10,H 4.60,N 2.12.)
进一步的，本发明涉及的所述深蓝光热活化延迟荧光材料可以用于构成电致发光器件中的发光层。
其中在一个具体实施方式中，所述电致发光器件包括玻璃和导电玻璃(ITO)衬底层、空穴传输和注入层(聚3，4-乙撑二氧噻吩：聚苯乙烯磺酸盐，PEDOT:PSS)、发光层3(本发明具有延迟荧光的主体材料和蓝光磷光客体Firpic)、电子传输层(1,3,5-三(3-(3-吡啶基)苯基)苯Tm3PyPB)以及阴极层5氟化锂/铝)
进一步的，在一个上述电致发光器件的具体制备方式中，其可以是在经过清洗的导电玻璃(ITO)衬底上依次旋涂：PESOT:PSS、热活化延迟荧光主体+磷光客体，然后在高真空条件下依次蒸镀TmPyPB、1nm的LiF和100nm的Al。
进一步的，分别结合了本发明涉及的所述化合物1、化合物2和化合物3的电致发光器件，其具体的器件结构如下：
器件1：ITO/PEDOT:PSS(50nm)/化合物1：Firpic(5％40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)
器件2：ITO/PEDOT:PSS(50nm)/化合物2：Firpic(5％40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)
器件3：ITO/PEDOT:PSS(50nm)/化合物3：Firpic(5％40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)
进一步的，对上述各电致发光器件进行性能测量，其中所述器件的电流-亮度-电压特性是由带有校正过的硅光电二极管的Keithley源测量系统(Keithley 2400 Sourcemeter、Keithley 2000 Currentmeter)完成的，电致发光光谱是由法国JY公司SPEX CCD3000光谱仪测量的，所有测量均在室温大气中完成。
各器件的性能数据见下表：
Figure PCTCN2019071069-appb-000016
本发明通过不同官能团的搭配，获得了一系列的具有显著TADF特性的深蓝光热活化延迟荧光材料，同时其合成路线设计合理，目标材料的合成效率高。
进一步的，采用由本发明涉及的所述深蓝光热活化延迟荧光材料制备出的有机电致发光器件，其发光效率高，器件效果优良。
本发明的技术范围不仅仅局限于上述说明中的内容，本领域技术人员可以在不脱离本发明技术思想的前提下，对上述实施例进行多种变形和修改，而这些变形和修改均应当属于本发明的范围内。

Claims (10)

  1. 一种深蓝光热活化延迟荧光材料；其中其构成化合物1的分子结构式如下：
    Figure PCTCN2019071069-appb-100001
  2. 根据权利要求1所述的一种深蓝光热活化延迟荧光材料，其中所述化合物1是通过中间体结合9,10-二氢-9,9-二甲基吖啶合成出的，其中所述中间体的分子结构式如下：
    Figure PCTCN2019071069-appb-100002
  3. 根据权利要求2所述的一种深蓝光热活化延迟荧光材料，其中所述化合物1是采用以下合成路线合成出的：
    Figure PCTCN2019071069-appb-100003
  4. 根据权利要求2所述的一种深蓝光热活化延迟荧光材料，其中所述中间体是以原料4-溴磷酮合成出的，其中所述4-溴磷酮的分子结构式如下：
    Figure PCTCN2019071069-appb-100004
  5. 根据权利要求4所述的一种深蓝光热活化延迟荧光材料，其中所述中间体是采用以下合成路线合成出的：
    Figure PCTCN2019071069-appb-100005
  6. 根据权利要求2所述的一种深蓝光热活化延迟荧光材料，其中所述9,10-二氢-9,9-二甲基吖啶衍生为9,10-二氢-9,9-二苯基吖啶，结合所述中间体，使得所述化合物1衍生为化合物2，所述化合物2的分子结构式如下：
    Figure PCTCN2019071069-appb-100006
  7. 根据权利要求6所述的一种深蓝光热活化延迟荧光材料，其中所述化合物2是采用以下合成路线合成出的：
    Figure PCTCN2019071069-appb-100007
  8. 根据权利要求2所述的一种深蓝光热活化延迟荧光材料，其 中所述9,10-二氢-9,9-二甲基吖啶衍生为9,10-二氢-9,9-二苯基硅代吖啶，结合所述中间体，使得所述化合物1衍生为化合物3，所述化合物3的分子结构式如下：
    Figure PCTCN2019071069-appb-100008
  9. 根据权利要求8所述的一种深蓝光热活化延迟荧光材料，其中所述化合物3是采用以下合成路线合成出的：
    Figure PCTCN2019071069-appb-100009
  10. 一种电致发光器件，其包括发光层；其中所述发光层的材料包括上述权利要求中任一项所述化合物1、化合物2或是化合物3中的至少一种。
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