CN113979903A - 一种含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料、制备方法及应用 - Google Patents
一种含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料、制备方法及应用 Download PDFInfo
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- CN113979903A CN113979903A CN202111347081.9A CN202111347081A CN113979903A CN 113979903 A CN113979903 A CN 113979903A CN 202111347081 A CN202111347081 A CN 202111347081A CN 113979903 A CN113979903 A CN 113979903A
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- C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
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Abstract
本发明公开了一种含有苯基砜‑螺芴结构单元的有机热活化延迟荧光材料,属于有机发光材料技术领域,所述的含有苯基砜‑螺芴结构单元的有机热活化延迟荧光材料采用芳香取代的胺基或芳香杂环胺基作为给体单元,苯基砜结构作为受体单元,以苯基砜作为强受体单元,有利于分子内电荷转移;此外,通过螺结构中sp3杂化的碳原子将给体与受体单元分离,形成面对面的几何构象,可以实现空间电荷转移,提高激子利用率。本发明制得的苯基砜‑螺芴结构单元的有机热活化延迟荧光材料,原料易得且成本低廉,合成简单高效,产物易纯化,产率较高,具有良好的空穴/电子传输性能,高的荧光量子产率,便于规模化生产,可广泛应用于有机电致发光器件领域。
Description
技术领域
本发明涉及有机发光材料技术领域,尤其涉及一种含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料、制备方法及其应用。
背景技术
有机发光二极管(OLED)作为“梦幻显示器”,近几十年来已经取得了巨大的突破,并且在全彩色显示领域得到了广泛的应用。OLED具有响应速度快、发热低、体积小、质量轻、自发光、功耗低、驱动电压低、材料来源广泛、成本低等一系列优点,且近年来其市场需求迅速增加,具有非凡的商业潜力。
OLED发光材料可大体分为三种,传统荧光材料、磷光材料和热活化延迟荧光(TADF)材料。由于自旋禁阻的原因,三线态激子不能直接辐射发光,传统荧光材料仅可利用单线态激子发光,理论最高量子效率仅为25%。磷光材料通过使用重金属原子配位,利用其强大的自旋轨道耦合作用打破了自旋禁阻,能够同时利用单线态和三线态激子发光,理论最高量子效率达到100%。TADF材料最开始由日本九州大学的Adachi课题组于2009年首次提出(A.Endo,M.Ogasawara,A.Takahashi,D.Yokoyama,Y.Kato,C.Adachi,Adv.Mater.2009,21,4802.),并于2012年取得巨大突破,通过提升反系间蹿越速率的方式实现三线态激子到单线态激子的转化,从而实现100%的内量子效率,避免了重金属元素的使用,合成成本低,相应器件效率与磷光器件相当,是有机光电领域当下的研究热点之一。
现阶段TADF材料绝大多数采用的都是D-π-A共轭型分子结构,容易发生聚集淬灭,器件效率衰减严重。而通过空间电荷转移实现TADF,可以更加有效地减少最高占据分子轨道(HOMO)和最低未占据分子轨道(LUMO)的重叠,但是目前这类材料的分子种类较少,需进行深入且***性的探究。
公开号为CN110862341A的中国专利文献中公开了一种具有聚集诱导发光(AIE)效应含二氰基乙烯基的咔唑类衍生物,以二氰基乙烯基为电子受体,咔唑基为电子供体,该发明化合物利用腈基团的强的吸电子能力,与咔唑衍生物相结合可以在分子内部产生空间位阻并导致分子构象扭曲,使其具有显著的AIE效应。
公开号为CN112225747A的中国专利文献中公开了一种热致延迟荧光性能的有机发光材料,该类有机发光材料以环芴酮二噻吩为骨架,通过连接不同的给体单元与受体单元,形成双极性有机小分子发光材料,可广泛应用于有机电致发光器件领域、防伪、化学生物检测、生物成像等领域。
发明内容
本发明提供了一种含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料,合成简单高效,具有良好的空穴/电子传输性能,高的荧光量子产率,便于规模化生产,可广泛应用于有机电致发光器件领域。
具体采用的技术方案如下:
一种含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料,具有式I-1~I-5所示结构:
其中,R为卤素,Ar为芳香取代的胺基、芳香杂环胺基。
优选的,所述的芳香杂环胺基为Ⅱ-1~Ⅱ-8所示结构:
所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料采用芳香取代的胺基或芳香杂环胺基作为给体单元,苯基砜结构作为受体单元,以苯基砜作为强受体单元,有利于分子内电荷转移;此外,通过螺结构中sp3杂化的碳原子将给体与受体单元分离,形成面对面的几何构象,可以实现空间电荷转移,提高激子利用率。
本发明还提供了所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料的制备方法,所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料由化合物A与化合物B反应后,再与化合物C反应得到;
所述的化合物C为Ⅲ-1~Ⅲ-9所示结构:
具体地,所述的制备方法包括以下步骤:
(1)将化合物A与化合物B在碱、氨基酸、铜催化剂和过氧化氢存在的条件下反应,得到中间体;
所述的中间体为Ⅳ-1~Ⅳ-3所示结构,其中,X1,X2,X3,X4,X5均为卤素,X4和X5为不同种卤素;
(2)将中间体与化合物C以摩尔比1:1~3在碱、钯催化剂和三叔丁基膦四氟硼酸盐存在的条件下反应得到I-1~I-5所示结构的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料。
具体地,所述的制备方法还包括以下步骤:
将如I-1、I-2、I-4所示结构的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料与化合物C以摩尔比1:1~1.5在碱、钯催化剂和三叔丁基膦四氟硼酸盐存在的条件下反应得到I-3或I-5所示结构的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料。
优选的,步骤(1)中,所述的中间体的制备方法包括以下步骤:
将化合物A与化合物B以摩尔比1:1~3在碱、氨基酸、铜催化剂和过氧化氢存在的条件下反应,得到如Ⅳ-1或Ⅳ-2所示结构的中间体;
或者,将如Ⅳ-1所示结构的中间体与另一种化合物B以摩尔比1:1~1.5在碱、氨基酸、铜催化剂和过氧化氢存在的条件下反应,得到如Ⅳ-3所示结构的中间体。
优选的,所述的碱为有机碱或金属碳酸盐;所述的氨基酸为甘氨酸;所述的铜催化剂为氯化亚铜、溴化亚铜或碘化亚铜;所述的钯催化剂为醋酸钯。
本发明还提供了所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料在光电领域的应用。
本发明还提供了一种由所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料制得的有机电致发光器件,包括导电玻璃衬底、空穴传输层、空穴注入层、有机发光层、电子注入层、电子传输层和阴极层,其特征在于:有机发光层含有所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料。
与现有技术相比,本发明的有益效果在于:
(1)本发明制得的含有苯基砜-螺芴单元结合的有机热活化延迟荧光材料,以芳香取代的胺基或芳香杂环胺基为给体单元,以苯基砜为受体单元,引入了芳香取代的胺基或芳香杂环胺基提高载流子迁移率,可以通过改变相应的芳香取代的胺基或芳香杂环胺基来对化合物的发光进行调控,且苯基砜-螺芴单元的结合可以被用来设计利用空间电荷转移作用,进一步改善材料的发光效率。
(2)本发明制得的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料,原料易得且成本低廉,合成简单高效,产物易纯化,产率较高,具有良好的空穴/电子传输性能,高的荧光量子产率,便于规模化生产,可广泛应用于有机电致发光器件领域。
(3)本发明利用所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料制得的电致发光器件性能优异,器件效率达到17.8%,远高于普通荧光器件。
附图说明
图1为实施例2制得的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料在甲苯溶液中的紫外-可见吸收光谱以及荧光光谱。
图2为实施例9制得的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料在甲苯溶液中的瞬态光致光谱衰变曲线图。
图3为应用例1中制得的有机电致发光器件的结构图,其中,1为导电玻璃衬底,2为空穴注入层,3为空穴传输层,4为有机发光层,5为电子传输层,6为电子注入层,7为阴极层。
具体实施方式
下面结合附图与实施例,进一步阐明本发明。应理解,这些实施例仅用于说明本发明,而不用于限制本发明的范围。
实施例1
中间体①的合成路线如下所示:
将9,9-双(4-碘苯基)-芴(2.0g,3.5mmol)、4-氟苯硫酚(0.45g,3.5mmol)、氢氧化钾(0.39g,7.0mmol)、碘化亚铜(0.04g,0.2mmol)和甘氨酸(0.05g,0.7mmol)溶解于60mL超干1,4-二氧六环溶剂中,加热回流16h,减压蒸馏,再加入60mL乙醇和40mL 30%过氧化氢溶液,加热回流24h,二氯甲烷和水萃取,柱层析纯化,得到中间体①,产物为白色固体(产率66%)。
本实施例中,所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料的合成路线如下所示:
将中间体①(1.5g,2.5mmol)、二苯胺(0.51g,3.0mmol)、叔丁醇钠(0.58g,6.0mmol)、醋酸钯(0.025g,0.1mmol)、三叔丁基膦四氟硼酸盐(0.087g,0.3mmol)和甲苯60mL一起加入150mL圆底烧瓶中,110℃下回流48h,二氯甲烷和水萃取,减压蒸馏,柱层析纯化,得到含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(产率90%)。
元素分析理论值C43H30FNO2S(%):C 80.23,H 4.70,F 2.95,N 2.18,O4.97,S4.98;发现值:C 80.20,H 4.72,F 2.94,N 2.18,O 4.97,S 4.97。
实施例2
中间体②的合成路线如下所示:
将9-(4-溴苯基)-9-(4-碘苯基)芴(1.84g,3.5mmol)、4-溴苯硫酚(0.67g,3.5mmol)、氢氧化钾(0.39g,7.0mmol)、碘化亚铜(0.04g,0.2mmol)和甘氨酸(0.05g,0.7mmol)溶解于60mL超干1,4-二氧六环溶剂中,加热回流16h,减压蒸馏,再加入60mL乙醇和40mL 30%过氧化氢溶液,加热回流24h,二氯甲烷和水萃取,柱层析纯化,得到中间体②,产物为白色固体(产率56%)。
本实施例中,所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料的合成路线如下所示:
将中间体②(1.5g,2.4mmol)、9,9’-二甲基吖啶(0.63g,3.0mmol)、叔丁醇钠(0.58g,6.0mmol)、醋酸钯(0.025g,0.1mmol)、三叔丁基膦四氟硼酸盐(0.087g,0.3mmol)和甲苯60mL一起加入150mL圆底烧瓶中,110℃下回流48h,二氯甲烷和水萃取,减压蒸馏,柱层析纯化,得到含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(产率84%)。
元素分析理论值C46H34BrNO2S(%):C 74.19,H 4.60,Br 10.73,N 1.88,O 4.30,S4.30;发现值:C 74.21,H 4.58,Br 10.70,N 1.89,O 4.30,S 4.29。
本实施例制得的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料在甲苯溶液中的紫外-可见吸收光谱以及荧光光谱如图1所示,图中的两条曲线分别紫外-可见吸收光谱(虚线)和荧光光谱(实线),其中荧光光谱的发射峰在375nm处,且半峰宽较窄,是一种近紫外光材料。
实施例3
利用实施例2制得的中间体②,以下式的路线合成所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料:
将中间体②(1.5g,2.4mmol)、咔唑(0.40g,2.4mmol)、叔丁醇钠(0.58g,6.0mmol)、醋酸钯(0.025g,0.1mmol)、三叔丁基膦四氟硼酸盐(0.087g,0.3mmol)和甲苯60mL一起加入150mL圆底烧瓶中,110℃下回流48h,二氯甲烷和水萃取,减压蒸馏,柱层析纯化,得到含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(产率87%)。
元素分析理论值C43H28BrNO2S(%):C 73.50,H 4.02,Br 11.37,N 1.99,O 4.55,S4.56;发现值:C 73.49,H 4.01,Br 11.35,N 2.00,O 4.55,S 4.55。
实施例4
利用实施例2制得的中间体②,以下式的路线合成所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料:
将中间体②(1.5g,2.4mmol)、吩噁嗪(1.11g,6.0mmol)、叔丁醇钠(1.16g,12.0mmol)、醋酸钯(0.05g,0.2mmol)、三叔丁基膦四氟硼酸盐(0.18g,0.6mmol)和甲苯90mL一起加入150mL圆底烧瓶中,110℃下回流48h,二氯甲烷和水萃取,减压蒸馏,柱层析纯化,得到含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(产率74%)。
元素分析理论值C55H36N2O4S(%):C 80.47,H 4.42,N 3.41,O 7.80,S3.91;发现值:C 80.49,H 4.40,N 3.40,O 7.80,S 3.90。
实施例5
利用实施例2制得的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料,以下式的路线合成本实施中的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料:
将实施例2制得的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(1.9g,2.5mmol)、5-苯基-5,10-二氢吩嗪(0.77g,3.0mmol)、叔丁醇钠(0.58g,6.0mmol)、醋酸钯(0.025g,0.1mmol)、三叔丁基膦四氟硼酸盐(0.087g,0.3mmol)和甲苯60mL一起加入150mL圆底烧瓶中,110℃下回流48h,二氯甲烷和水萃取,减压蒸馏,柱层析纯化,得到含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(产率81%)。
元素分析理论值C64H47N3O2S(%):C 83.36,H 5.14,N 4.56,O 3.47,S3.48;发现值:C 83.33,H 5.12,N 4.54,O 3.48,S 3.50;
实施例6
中间体③的合成路线如下所示:
利用实施例2制得的中间体①,将中间体①(2.0g,3.3mmol)、4-溴苯硫酚(0.81g,4.3mmol)、氢氧化钾(0.37g,6.6mmol)、碘化亚铜(0.04g,0.2mmol)和甘氨酸(0.05g,0.7mmol)溶解于60mL超干1,4-二氧六环溶剂中,加热回流24h,减压蒸馏,再加入60mL乙醇和40mL 30%过氧化氢溶液,加热回流24h,二氯甲烷和水萃取,柱层析纯化,得到中间体③,产物为白色固体(产率80%)。
本实施例中,所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料的合成路线如下所示:
将中间体③(1.7g,2.5mmol)、二苯胺(0.51g,3.0mmol)、叔丁醇钠(0.58g,6.0mmol)、醋酸钯(0.025g,0.1mmol)、三叔丁基膦四氟硼酸盐(0.087g,0.3mmol)和甲苯60mL一起加入150mL圆底烧瓶中,110℃下回流48h,二氯甲烷和水萃取,减压蒸馏,柱层析纯化,得到含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(产率90%)。
元素分析理论值C49H34FNO4S2(%):C 75.08,H 4.37,F 2.42,N 1.79,O8.16,S8.18;发现值:C 75.05,H 4.38,F 2.42,N 1.78,O 8.16,S 8.16。
实施例7
利用实施例6制得的中间体③,以下式的路线合成所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料:
将中间体③(1.7g,2.5mmol)、咔唑(0.59g,3.5mmol)、叔丁醇钠(0.58g,6.0mmol)、醋酸钯(0.025g,0.1mmol)、三叔丁基膦四氟硼酸盐(0.087g,0.3mmol)和甲苯60mL一起加入150mL圆底烧瓶中,110℃下回流48小时,二氯甲烷和水萃取,减压蒸馏,柱层析纯化,得到含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(产率90%)。
元素分析理论值C49H32FNO4S2(%):C 75.27,H 4.13,F 2.43,N 1.79,O8.18,S8.20;发现值:C 75.30,H 4.12,F 2.43,N 1.79,O 8.18,S 8.20。
实施例8
利用实施例6制得的中间体③,以下式的路线合成所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料:
将中间体③(1.7g,2.5mmol)、亚氨基芪(0.58g,3.0mmol)、叔丁醇钠(0.58g,6.0mmol)、醋酸钯(0.025g,0.1mmol)、三叔丁基膦四氟硼酸盐(0.087g,0.3mmol)和甲苯60mL一起加入150mL圆底烧瓶中,110℃下回流48小时,二氯甲烷和水萃取,减压蒸馏,柱层析纯化,得到含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(产率77%)。
元素分析理论值C51H34FNO4S2(%):C 75.82,H 4.24,F 2.35,N 1.73,O7.92,S7.94;发现值:C 75.80,H 4.22,F 2.34,N 1.73,O 7.94,S 7.94。
实施例9
中间体④的合成路线如下所示:
将9,9-双(4-碘苯基)-芴(2.0g,3.5mmol)、4-溴苯硫酚(1.34g,7.0mmol)、氢氧化钾(0.8g,14.4mmol)、碘化亚铜(0.06g,0.4mmol)和甘氨酸(0.05g,0.7mmol)溶解于90mL超干1,4-二氧六环溶剂中,加热回流48h,减压蒸馏,再加入40mL乙醇和80mL 30%过氧化氢溶液,加热回流24h,二氯甲烷和水萃取,柱层析纯化,得到中间体④,产物为白色固体(产率56%)。
本实施例中,所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料的合成路线如下所示:
将中间体④(1.7g,2.5mmol)、9,9’-二甲基吖啶(0.53g,3.0mmol)、叔丁醇钠(0.58g,6.0mmol)、醋酸钯(0.025g,0.1mmol)、三叔丁基膦四氟硼酸盐(0.087g,0.3mmol)和甲苯60mL一起加入150mL圆底烧瓶中,110℃下回流48h,二氯甲烷和水萃取,减压蒸馏,柱层析纯化,得到含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(产率60%)。
元素分析理论值C52H38BrNO4S2(%):C 70.58,H 4.33,Br 9.03,N 1.58,O 7.23,S7.25;发现值:C 70.60,H 4.35,Br 9.05,N 1.59,O 7.21,S 7.25。
本实施例制得的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料在甲苯溶液中的瞬态光致光谱衰变曲线图如图2所示,图中的两条曲线分别为有氧条件和无氧条件下的瞬态光致光谱衰变曲线,可以观察到显著的TADF特征,且寿命较短。
实施例10
利用实施例6制得的中间体④,以下式的路线合成所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料:
将中间体④(2.3g,3.0mmol)、吩噁嗪(1.28g,7.0mmol)、叔丁醇钠(1.16g,12.0mmol)、醋酸钯(0.05g,0.2mmol)、三叔丁基膦四氟硼酸盐(0.18g,0.6mmol)和甲苯90mL一起加入150mL圆底烧瓶中,110℃下回流48h,二氯甲烷和水萃取,减压蒸馏,柱层析纯化,得到含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(产率71%)。
元素分析理论值C61H40N2O6S2(%):C 76.23,H 4.20,N 2.91,O 9.99,S6.67;发现值:C 76.22,H 4.21,N 2.90,O 9.99,S 6.64。
实施例11
利用实施例9制得的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料,以下式的路线合成所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料:
将实施例9制得的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料(2.1g,2.4mmol)、吩噁嗪(0.53g,2.9mmol)、叔丁醇钠(0.58g,6.0mmol)、醋酸钯(0.025g,0.1mmol)、三叔丁基膦四氟硼酸盐(0.09g,0.3mmol)和甲苯90mL一起加入150mL圆底烧瓶中,110℃下回流48h,二氯甲烷和水萃取,减压蒸馏,柱层析纯化,得到化合物XI(产率74%)。
元素分析理论值C64H46N2O5S2(%):C 77.87,H 4.70,N 2.84,O 8.10,S6.50;发现值:C 77.92,H 4.71,N 2.84,O 8.11,S 6.51。
应用例1
利用所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料制得的有机电致发光器件结构为:ITO/MoO3(8nm)/TAPC(50nm)/mcP:5%Emitters(本发明化合物)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)。
如图3所示,所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料制得的有机电致发光器件,包括导电玻璃衬底1,空穴注入层2(三氧化钼MoO3),空穴传输层3(4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]TAPC),有机发光层4(mCP主体材料和本发明制得的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料),电子传输层5(3,3'-[5'-[3-(3-吡啶基)苯基][1,1':3',1”-三联苯]-3,3”-二基]二吡啶TmPyPB),电子注入层6(氟化锂LiF),7为阴极层(铝Al)。
器件制备过程如下:电致发光器件按本领域已知方法制作,如按参考文献(Adv.Mater.2004,16,537.)公开的方法制作;具体方法为:在高真空条件下,在经过清洗的导电玻璃(ITO)衬底上依次蒸镀8nm的MoO3,50nm的TAPC,20nm的发光层,40nm的TmPyPB,1nm的LiF和120nm的Al。
器件性能测试数据见下表:
由上表可知,应用本发明化合物的器件最大电流效率可达28.7cd/A,启动电压最低仅为3.6V,效率衰减性能较好,且量子效率也高于应用传统荧光材料的器件。
与其他的荧光材料相比,本发明采用了苯基砜-螺芴单元结合的结构,在应用了空间电荷转移性质的同时,可以通过改变相应的芳香取代的胺基或芳香杂环胺基来对化合物的发光进行调控,且采用的原料均可通过实验室内的简单方法进行合成或者从市场上直接购买获得,合成路线简单高效,适用于大规模实际生产。且本发明的电致发光器件量子效率较高,效率衰减性能较好,可以应用于OLED显示领域。
以上所述的实施例对本发明的技术方案进行了详细说明,应理解的是以上所述的仅为本发明的具体实施例,并不用于限制本发明,凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等,均应包含在本发明的保护范围之内。
Claims (9)
6.根据权利要求5所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料的制备方法,其特征在于,所述的制备方法还包括以下步骤:
将如I-1、I-2、I-4所示结构的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料与化合物C以摩尔比1:1~1.5在碱、钯催化剂和三叔丁基膦四氟硼酸盐存在的条件下反应得到I-3或I-5所示结构的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料。
7.根据权利要求5所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料的制备方法,其特征在于,步骤(1)中,所述的中间体的制备方法包括以下步骤:
将化合物A与化合物B以摩尔比1:1~3在碱、氨基酸、铜催化剂和过氧化氢存在的条件下反应,得到如Ⅳ-1或Ⅳ-2所示结构的中间体;
或者,将如Ⅳ-1所示结构的中间体与另一种化合物B以摩尔比1:1~1.5在碱、氨基酸、铜催化剂和过氧化氢存在的条件下反应,得到如Ⅳ-3所示结构的中间体。
8.根据权利要求5所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料的制备方法,其特征在于,所述的碱为有机碱或金属碳酸盐;所述的氨基酸为甘氨酸;所述的铜催化剂为氯化亚铜、溴化亚铜或碘化亚铜;所述的钯催化剂为醋酸钯。
9.根据权利要求1~3任一所述的含有苯基砜-螺芴结构单元的有机热活化延迟荧光材料在光电领域的应用。
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