CN110467561B - 基于二苯砜的双发色团热活性延迟荧光材料的合成及应用 - Google Patents
基于二苯砜的双发色团热活性延迟荧光材料的合成及应用 Download PDFInfo
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- CN110467561B CN110467561B CN201910649806.6A CN201910649806A CN110467561B CN 110467561 B CN110467561 B CN 110467561B CN 201910649806 A CN201910649806 A CN 201910649806A CN 110467561 B CN110467561 B CN 110467561B
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Images
Classifications
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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Abstract
本发明公开了一类含双发色团的热活性延迟荧光材料及其在溶液加工型有机电致发光器件中的应用。本发明以咔唑‑二苯砜蓝光发色团为末端基团，以三苯胺‑蒽醌橙红光发色团为中心核，通过非共轭和共轭连接方式构筑含双发色团热活性延迟荧光材料。这类材料有利于分离分子的最高占据轨道和最低空轨道的空间分布，获得较小的单/三线态间的能隙差；并且这类材料的分子内能量传递随连接方式的改变而变化，实现单一分子的双重发射。本发明将这类双发色团热活性延迟荧光材料用作溶液加工型有机电致发光二极管的发光层材料，器件获得了最大外量子效率3.96%。
Description
技术领域
本发明涉及一类基于二苯基砜单元的双发色团热活性延迟荧光材料，特别涉及一种以TADF(热活性延迟荧光)红光材料为核，TADF蓝光材料为末端的单分子双发射热活性延迟材料，及其作为溶液加工型有机电致发光二极管的发光层材料的应用，属于有机电致发光材料技术领域。
技术背景
热活性延迟荧光(TADF)材料不含金属原子，且可充分利用单线态和三线态激子发光，其内量子效率达100％，被誉为第三代有机电致发光材料。近年来，TADF材料获得了巨大的发展，其结构一般由电子给体(D)单元与电子受体(A)单元通过共轭连接方式构筑具有扭曲结构的D-A型分子。但这类TADF分子通常在溶液和固体薄膜中仅呈现出单发射峰，并且其半峰宽较宽。因此，构筑单分子双发射材料对研究白光材料具有重要的基础研究意义。
分子内能量传递过程是一个非常活跃的研究领域。单分子内不同发色团间的分子内三线态能量转移的研究引起了人们的特别关注。光化学里描述“分子内的能量传递”是指一个分子的给体(D)处于激发态时，通过能量传递使受体(A)激发到高能级的激发态，而自身失活回到能级较低的状态。当引入氧原子或烷氧基后，能量传递的通道被阻断，各发色团保持自身的发射光谱，因而单分子可呈现宽光谱的发射。
鉴于以上原因，本发明旨在构筑单分子双发射TADF材料，为获得单分子白光材料提供研究基础。因此，本发明设计合成了系列基于咔唑-二苯砜的蓝光发色团和三苯胺-蒽醌的橙红光发色团的双发色团热活性延迟荧光材料；通过在蓝光发色团和红光发色团间引入氧原子和烷氧基链，研究两个发色团之间的能量传递过程；进一步在咔唑基团上引入溴原子，探究重原子效应对该系列发光材料光物理性能的影响。
发明内容
目前，针对多发色团构筑单分子双发射TADF材料的研究缺乏，本发明的目的是在于提供一种基于咔唑-二苯砜的蓝光发色团和三苯胺-蒽醌的橙红光发色团构筑的双发色团单分子双发射TADF材料。
本发明的另一个目的是在于提供这类双发色团单分子双发射TADF材料作为溶液加工型有机电致发光二极管发光层材料的应用。
为了实现上述技术目的，本发明提供了一类基于咔唑-二苯砜的蓝光发色团和三苯胺-蒽醌的橙红光发色团构筑的双发色团单分子双发射TADF材料，其具有M1～M5结构：
M1～M5以基于三苯胺-蒽醌的橙红光发色团为中心单元，以基于咔唑-二苯砜的蓝光发色团为末端单元，通过非共轭和共轭方式构筑含双发色团TADF材料。在这类材料中，蓝光发色团与橙红光发色团之间的能量传递随连接方式的改变而变化，从而实现单分子双发射。
另一方面，本发明还提供了所述的双发色团TADF材料的应用，将其作为有机电致发光二极管的发光层材料，用于溶液加工型有机电致发光器件。
相对现有技术，本发明的技术方案带来的有益效果在于：
现有报道大都是通过电子给体和电子受体共轭连接构筑仅含单一发色团的TADF材料。本发明利用共轭和非共轭两种连接方式，将蓝光发色团和橙红光发色团连接起来，构筑含有双发色团的TADF材料。这类材料有利于分离分子的HOMO与LUMO分布，获得较小的ΔEST；并且这类材料的分子内能量传递随连接方式的改变而变化，实现单一分子的双重发射，有利于获得单分子白光材料。
本发明将这类双发色团热活性延迟荧光材料用作溶液加工型有机电致发光二极管的发光层材料，器件获得了最大外量子效率3.96％。
附图说明
图1为本发明实施例1制得的化合物M1～M5的热失重曲线。
图2为本发明实施例1制得的化合物M1～M5在溶液中的电化学曲线。
图3为本发明实施例1制得的化合物M1～M5在甲苯溶液(10-5M)中的紫外可见吸收光谱。
图4为本发明实施例1制得的化合物M1～M5在甲苯溶液(10-5M)中的光致发光光谱。
图5为本发明实施例1制得的化合物M1～M5在固体薄膜中的光致发光光谱。
图6为本发明实施例1制得的化合物M1～M5的器件电致发光光谱。
图7为本发明实施例1制得的化合物M1～M5的器件外量子效率-电流密度曲线图。
具体实施方式
以下具体实施案例旨在对本发明进一步说明，但这些具体实施方案不以任何方式限制本发明的保护范围。
实施例1
化合物3a的合成
将化合物1(5.0g，0.03mol)、NaH(1.44g，0.06mol)和100mL干燥的N,N-二甲基甲酰胺(DMF)依次加入250mL三口烧瓶中，混合物在氮气氛中于室温下搅拌30min；加入化合物2(7.62g，0.03mol)后，升温至100℃搅拌4h。待反应液冷却至室温，倒入大量的水中，析出白色固体。抽滤、固体依次经乙醇和乙醚洗涤、干燥，所得白色固体进一步通过柱层析提纯，以石油醚/二氯甲烷(V/V；2:1)为洗脱剂得到白色固体化合物3a(3.85g,产率:32％)。1H NMR(400MHz,CDCl3)δ8.15(dd,J＝11.0,8.2Hz,2H),8.07(dd,J＝8.8,5.0Hz,1H),7.77(d,J＝8.6Hz,1H),7.43(q,J＝8.3Hz,2H),7.37-7.29(m,1H),7.26(t,J＝8.5Hz,1H).
化合物3b的合成
合成方法同化合物3a，化合物3b为白色固体，产率为40％。1H NMR(400MHz,CDCl3)δ8.23(d,J＝1.9Hz,1H),8.19-8.13(m,2H),8.10-8.01(m,3H),7.76-7.68(m,2H),7.48(dd,J＝8.7,1.9Hz,1H),7.45-7.38(m,2H),7.36-7.29(m,1H),7.29-7.21(m,3H).
化合物4a的合成
将中间体3a(3.0g，7.5mmol)、KOH(1.26g，22.5mmol)、50mL二甲基亚砜和3mL蒸馏水依次加入100mL三口烧瓶中，混合物在75℃下搅拌20h。待反应液冷却至室温后，倒入水中；加入KOH溶液调至碱性，水层用二氯甲烷洗(3×100mL)，分出水层，酸化后析出白色固体，倒入分液漏斗，乙酸乙酯萃取(3×50mL),合并萃取液，经水洗、干燥、过滤后，除去溶剂并烘干得白色固体化合物4a(2.9g，产率:97％)。1H NMR(400MHz,DMSO)δ10.72(s,1H),8.25(d,J＝7.7Hz,2H),8.16(d,J＝8.6Hz,2H),7.89(dd,J＝8.7,2.1Hz,4H),7.49(d,J＝8.2Hz,2H),7.46-7.38(m,2H),7.33(d,J＝7.6Hz,2H),6.99(d,J＝8.8Hz,2H).
化合物4b的合成
合成方法同化合物4a，化合物4b为白色固体，产率为95％。1H NMR(400MHz,DMSO)δ10.74(s,1H),8.52(d,J＝1.9Hz,1H),8.31(d,J＝7.8Hz,1H),8.16(d,J＝8.6Hz,2H),7.88(dd,J＝8.7,1.7Hz,4H),7.60-7.38(m,4H),7.34(dd,J＝7.8,1.8Hz,1H),6.99(d,J＝8.8Hz,2H).
化合物5a的合成
向100mL三口瓶中，依次加入中间4a(3.0g，7.5mmol)、1,2-二溴乙烷(7g，37.7mmol)、K2CO3(1.37g，10mmol)和50mL N,N-二甲基甲酰胺，混合物在100℃下搅拌3h。待反应液冷却至室温，倒入水中，用乙酸乙酯萃取(3×50mL)；有机相经饱和食盐水洗涤(3×100mL)、无水MgSO4干燥、过滤；剩余物以石油醚/二氯甲烷(V/V；1:2)为洗脱剂经柱层析分离得到白色固体化合物5a。(1.6g,产率:42％)。1H NMR(400MHz,CDCl3)δ8.14(dd,J＝7.9,6.3Hz,4H),7.99(d,J＝8.9Hz,2H),7.74(d,J＝8.6Hz,2H),7.48-7.37(m,4H),7.37-7.28(m,2H),7.05(d,J＝8.9Hz,2H),4.36(t,J＝6.1Hz,2H),3.66(t,J＝6.1Hz,2H).MALDI-MS(m/z)of C26H19BrNO3S for[M+]:calcd.505.03；found,505.07.
化合物5b的合成
合成方法同化合物5a，化合物5b为白色固体，产率为45％。1H NMR(400MHz,CDCl3)δ8.23(d,J＝1.8Hz,1H),8.20-8.11(m,2H),8.07(d,J＝7.8Hz,1H),8.04-7.93(m,2H),7.74-7.65(m,2H),7.48(dd,J＝8.7,1.9Hz,1H),7.45-7.37(m,2H),7.36-7.27(m,2H),7.11-6.99(m,2H),4.36(t,J＝6.1Hz,2H),3.66(t,J＝6.1Hz,2H).MALDI-MS(m/z)of C26H19Br2NO3Sfor[M+]:calcd.582.95；found,584.97.
化合物8的合成
向250mL三口烧瓶中依次加入化合物6(5.0g，0.02mol)、化合物7(7.1g，0.03mol)、1,10-菲罗啉(1.1g，6.0mmol)和甲苯100mL；然后在氮气中110℃下加入CuI(1.15g，6mmol)和KOH(10.75g，0.19mol)，混合物在135℃下搅拌反应过夜。待反应液冷却至室温，减压旋除甲苯溶剂，加入100mL二氯甲烷，混合物依次经饱和食盐水洗涤(3×100mL)、无水MgSO4干燥、过滤、减压蒸馏，残余物以石油醚/二氯甲烷(V/V；10:1)为洗脱剂经柱层析分离得到无色稠状物化合物8(3.9g，产率:55％)。1H NMR(400MHz,CDCl3)δ7.26(ddd,J＝21.7,11.4,4.7Hz,4H),7.05(dd,J＝11.8,5.0Hz,4H),6.98(s,1H),6.93-6.81(m,4H),3.80(s,3H).
化合物9的合成
将化合物8(4.5g，12.75mmol)、联硼酸频那醇酯(3.56g，14mmol)、醋酸钾(5.0g，51mmol)和1,1'-双二苯基膦二茂铁二氯化钯(0.28g，0.38mmol)溶于80mL二氧六环中，在氮气保护下，混合物在80℃搅拌反应24h。待反应液冷却至室温，减压旋除二氧六环溶剂，加入二氯甲烷(100mL)，有机相经水洗(3×100mL)、干燥、过滤和减压蒸馏除去溶剂，剩余物通过柱层析分离纯化，以石油醚/二氯甲烷(V/V；2:1)洗脱得到无色稠状物9(3.6g，产率:70％)。1HNMR(400MHz,CDCl3)δ7.63(d,J＝8.5Hz,2H),7.30-7.17(m,2H),7.13-7.04(m,4H),6.97(d,J＝8.5Hz,3H),6.84(d,J＝8.9Hz,2H),3.81(s,3H),1.33(s,12H).
化合物10的合成
向500mL的三口瓶依次投入化合物9(5.53g，13.8mmol)、2,6-二溴蒽醌(2.4g，6.57mmol)、四三苯基膦钯(227mg，0.20mmol)、K2CO3[2M]118mL和四氢呋喃200mL，混合物在氮气下85℃搅拌24h。待反应液冷却至室温，减压旋除溶剂，加入三氯甲烷100mL，有机相依次经水洗(3×150mL)、无水MgSO4干燥、过滤和减压蒸馏除去溶剂，粗产物以石油醚/二氯甲烷(V/V；2:3)为洗脱剂经柱层析分离纯化得到红棕色固体10(2.84g，产率:57％)。1H NMR(400MHz,CDCl3)δ8.51(d,J＝1.9Hz,2H),8.35(d,J＝8.2Hz,2H),7.97(dd,J＝8.2,1.9Hz,2H),7.60(d,J＝8.7Hz,4H),7.33-7.22(m,4H),7.13(dd,J＝12.8,5.8Hz,12H),7.04(t,J＝7.3Hz,2H),6.93-6.85(m,4H),3.83(s,6H).MALDI-MS(m/z)of C52H38N2O4 for[M+]:calcd.754.28；found,756.38.
化合物11的合成
室温下，在250mL的三口瓶中加入化合物10(1g，1.32mmol)和干燥的二氯甲烷100mL；然后在-78℃下加入1mL三溴化硼，混合物在-78℃下搅拌2h后，升温至室温继续搅拌24h。加入10mL饱和碳酸氢钠淬灭反应，减压旋除溶剂；加入乙酸乙酯100mL，有机相经水洗、减压蒸馏旋除溶剂；残余物以二氯甲烷/乙酸乙酯(V/V；10:1)为洗脱剂经柱层析分离纯化得到红棕色固体(200mg，产率:20％)。1H NMR(400MHz,DMSO)δ9.52(s,2H),8.37-8.00(m,6H),7.66(d,J＝8.0Hz,4H),7.31(t,J＝7.6Hz,4H),7.20-6.87(m,14H),6.80(d,J＝8.4Hz,4H).MALDI-MS(m/z)of C50H34N2O4 for[M+]:calcd.726.25；found,727.60.
化合物13的合成
在100mL的三口瓶中依次加入化合物12(10g，39mmol)、氟苯(3.76g，39mmol)和无水AlCl3(5.73g，43mmol)；混合物在氮气氛中于90℃搅拌反应90min。待反应液冷却至室温，倒入水中；混合物用二氯甲烷萃取(3×30mL)，收集的有机相经水洗(3×100mL)、无水MgSO4干燥、过滤和减压除去溶剂，得到白色固体中间体13(12g，产率:98％)。1H NMR(400MHz,CDCl3)δ7.99-7.90(m,2H),7.83-7.74(m,2H),7.69-7.60(m,2H),7.24-7.13(m,2H).
化合物14的合成
合成方法同化合物3a，化合物14为白色固体，产率90％。1H NMR(400MHz,CDCl3)δ8.18-8.09(m,4H),7.95-7.86(m,2H),7.81-7.68(m,4H),7.42(tt,J＝8.2,4.2Hz,4H),7.32(ddd,J＝8.0,6.6,1.6Hz,2H).
化合物15的合成
合成方法同化合物9，化合物无15为白色固体，产率76％。1H NMR(400MHz,CDCl3)δ8.15(dd,J＝16.1,8.2Hz,4H),8.01(q,J＝8.3Hz,4H),7.74(d,J＝8.6Hz,2H),7.47-7.36(m,4H),7.36-7.27(m,2H),1.35(s,12H).MALDI-MS(m/z)of C30H28BNO4S for[M+]:calcd.509.18；found,509.21.
化合物17的合成
合成方法同化合物9，化合物17为白色固体，产率63％。1H NMR(400MHz,CDCl3)δ8.74(s,2H),8.30(d,J＝7.7Hz,2H),8.20(d,J＝7.7Hz,2H),1.38(s,24H).
化合物19的合成
合成方法同化合物8，化合物19为无色稠状物，产率32％。1H NMR(400MHz,CDCl3)δ7.51(d,J＝8.5Hz,2H),7.34(d,J＝8.6Hz,2H),7.30-7.21(m,3H),7.06(t,J＝6.6Hz,3H),6.94(d,J＝8.7Hz,2H),6.81(d,J＝8.6Hz,2H).
化合物20的合成
向250mL的三口烧瓶中依次加入化合物19(2.7g，6mmol)、化合物17(1.25g，2.73mmol)、K2CO3[2M]13.5mL、四三苯基膦钯(94mg，0.08mmol)和100mL甲苯以及20mL乙醇，混合物在氮气保护中于85℃搅拌反应12h。待反应液冷却至室温，减压旋除溶剂，加入100mL二氯甲烷，有机相经水洗(3×100mL)、无水MgSO4干燥、过滤和减压除去溶剂；粗产品以石油醚/二氯甲烷(V/V；4:1)为洗脱剂经柱层析分离纯化得到红色固体10(1.30g，产率:56％)。1H NMR(400MHz,CDCl3)δ8.51(d,J＝1.6Hz,2H),8.36(d,J＝8.1Hz,2H),7.98(dd,J＝8.2,1.7Hz,2H),7.63(d,J＝8.6Hz,4H),7.39(d,J＝8.7Hz,4H),7.32(t,J＝7.8Hz,4H),7.13(dt,J＝16.0,8.0Hz,10H),7.03(d,J＝8.7Hz,4H).MALDI-MS(m/z)of C50H32Br2N2O2 for[M+]:calcd.850.08；found,854.13.
化合物M1的合成
向50mL的三口烧瓶中依次加入化合物3a(220mg，0.55mmol)、化合物11(200mg，0.275mmol)、NaOH(55mg，1.375mmol)、CuI(21mg，0.11mmol)和N,N-二甲基甲酰胺30mL，混合物在氮气保护下于160℃回流过夜。待反应液冷却至室温，减压蒸馏除掉溶剂，加入三氯甲烷50mL，有机相经水洗(3×100mL)、无水MgSO4干燥、过滤和减压除去溶剂；粗产品以石油醚/二氯甲烷(V/V；1:5)为洗脱剂，经柱层析分离纯化得到橙红色固体M1(200mg,产率:48％)。1H NMR(400MHz,CDCl3)δ8.51(d,J＝1.5Hz,2H),8.35(d,J＝8.2Hz,2H),8.15(dd,J＝18.9,8.1Hz,8H),8.04-7.96(m,6H),7.75(d,J＝8.6Hz,4H),7.64(d,J＝8.7Hz,4H),7.43(dd,J＝10.5,7.9Hz,10H),7.36-7.29(m,8H),7.21-7.12(m,16H),7.02(d,J＝8.9Hz,4H).13C NMR(100MHz,CDCl3)δ182.92,162.47,150.43,148.52,147.01,146.11,144.41,142.26,140.14,139.93,134.64,134.08,132.56,132.25,131.68,131.31,130.16,129.58,129.32,128.30,128.14,127.04,126.56,126.41,126.28,125.88,124.90,124.67,123.90,123.29,122.88,121.57,121.49,120.87,120.50,117.72,117.63,109.54.MALDI-MS(m/z)of C98H64N4O8S2 for[M+]:calcd.1488.42；found,1489.75.
化合物M2的合成
合成方法同化合物M1，化合物M2为橙红色固体，产率53％。1HNMR(400MHz,)δ8.50(d,J＝1.7Hz，2H),8.34(d,J＝8.1Hz，2H),8.19(dd,J＝17.6,5.2Hz，6H),8.06-7.95(m，8H),7.67(dd,J＝26.7,8.7Hz，8H),7.49-7.41(m，6H),7.30(dd,J＝15.3,8.2Hz，8H),7.16(dd,J＝14.1,8.1Hz，18H),7.02(d,J＝8.9Hz,4H).13C NMR(100MHz,CDCl3))δ182.91,162.55,150.38,148.51,147.01,146.10,144.45,141.73,140.63,140.30,138.65,134.48,134.08,132.27,131.68,131.31,130.20,129.59,129.43,128.94,128.15,127.05,126.40,125.65,124.92,124.67,123.91,123.28,122.90,122.77,121.50,121.25,120.69,117.64,113.63,111.03,109.76.MALDI-MS(m/z)of C98H62Br2N4O8S2 for[M+]:calcd.1644.24；found,1645.93.
化合物M3的合成
向50mL的三口烧瓶中依次加入化合物5a(347mg，0.69mmol)、化合物11(200mg，0.27mmol)、K2CO3(190mg，1.37mmol)和N,N-二甲基甲酰胺30mL，混合物在100℃下搅拌反应3h；待反应液冷却至室温，减压蒸馏除掉溶剂，加入三氯甲烷50mL，有机相经水洗(3×100mL)、无水MgSO4干燥、过滤和减压除去溶剂；残余物以二氯甲烷为洗脱剂经柱层析分离纯化得到红棕色固体M3(250mg,产率:57％)。M3的1H NMR(400MHz,CDCl3)δ8.50(s,2H),8.34(d,J＝8.2Hz,2H),8.14(dd,J＝12.2,8.1Hz,8H),7.98(dd,J＝17.1,8.6Hz,6H),7.74(d,J＝8.5Hz,4H),7.60(d,J＝8.7Hz,4H),7.46-7.36(m,8H),7.32(dd,J＝17.2,9.4Hz,8H),7.16-7.08(m,14H),7.05(t,J＝7.4Hz,2H),6.99(d,J＝8.6Hz,1H),6.92(d,J＝8.8Hz,4H),4.39(dd,J＝17.9,5.1Hz,8H).MALDI-MS(m/z)of C102H72N4O10S2(M3)for[M+]:calcd.1576.47；found,1577.03.
化合物M4的合成
合成方法同化合物M3，化合物M4为红棕色固体，产率34％。1H NMR(400MHz,CDCl3)δ8.49(s,2H),8.33(d,J＝8.2Hz,2H),8.22(s,2H),8.16(d,J＝8.5Hz,4H),8.06(d,J＝7.9Hz,2H),7.98(dd,J＝16.6,8.5Hz,6H),7.70(d,J＝8.5Hz,4H),7.60(d,J＝8.7Hz,4H),7.50-7.39(m,6H),7.38-7.22(m,9H),7.17-7.08(m,14H),7.05(t,J＝7.4Hz,2H),6.99(d,J＝8.7Hz,1H),6.91(d,J＝8.8Hz,4H),4.39(dd,J＝17.3,5.0Hz,8H).13C NMR(100MHz,CDCl3)δ183.04,162.71,155.26,148.95,147.29,141.63,140.96,140.36,138.72,134.12,133.94,133.14,132.31,131.28,130.15,129.32,128.94,128.09,127.96,127.61,127.09,125.65,125.14,124.54,124.20,123.28,122.77,122.32,121.77,121.23,120.69,115.79,115.68,115.33,113.60,111.06,109.79.MALDI-MS(m/z)of C102H70Br2N4O10S2 for[M+]:calcd.1732.29；found,1736.25.
化合物M5的合成
合成方法同化合物20，化合物M5为橙红色固体，产率90％。1H NMR(400MHz,CDCl3)δ8.54(d,J＝1.8Hz,2H),8.38(d,J＝8.1Hz,2H),8.21(d,J＝8.6Hz,4H),8.11(dd,J＝15.5,8.1Hz,8H),8.00(dd,J＝8.2,1.9Hz,2H),7.77(d,J＝8.5Hz,8H),7.67(d,J＝8.7Hz,4H),7.54(d,J＝8.7Hz,4H),7.42(ddd,J＝10.3,9.3,4.4Hz,8H),7.38-7.29(m,8H),7.26-7.19(m,12H),7.15(t,J＝7.3Hz,2H).13C NMR(100MHz,CDCl3)δ182.89,148.13,147.94,146.74,146.06,145.69,142.35,139.93,139.21,134.07,133.04,132.88,131.75,131.41,129.65,129.47,128.4,128.2,128.10,127.42,127.06,126.28,125.54,124.76,124.33,123.95,123.9,123.87,120.87,120.49,109.57.MALDI-MS(m/z)of C98H64N4O6S2 for[M+]:calcd.1457.43；found,1457.33.
实施例2
化合物M1-M5的热失重曲线如图1所示，其热分解温度分别为480，447，402，393，549℃。根据对应的分子结构以及热分解温度的变化趋势可以得出如下结论：引入卤原子溴和插入氧原子或烷氧基都在一定程度上降低了化合物的热分解温度Td。从结构上可以解释为碳-溴键具有较低的离解能，因此M1～M4的热分解温度变化趋势为M2＜M1，M4＜M3；进一步随着氧原子和烷氧基的插入，降低了分子的刚性结构，因此M3和M4的Td均比M1和M2低。M5具有最大的共轭结构，因此其热分解温度为最高的549℃。
实施例3
为了研究化合物M1～M5的电化学性能，我们利用循环伏安法对化合物的三氯甲烷溶液进行测试。如图2所示(插图为Fc/Fc+的CV曲线)，化合物M1～M5在电压为-1.5～2.0V的区间内均呈现出不可逆的氧化还原电位。根据氧化电位(Eox)和还原电位(Ered)值，由公式E(HOMO)(eV)＝－(Eox.vsFc/Fc++4.8)eV；E(LUMO)(eV)＝－(Ered.vsFc/Fc++4.8)eV；Eox.vsFc/Fc+＝(Eox－0.50)V和Ered.vsFc/Fc+＝(Ered－0.50)V(其中实际测试过程中Fc/Fc+相对于Ag/AgCl的电位为0.50V)计算得出M1～M5的HOMO能级分别为-5.4，-5.12，-5.15，-5.75，-5.4eV；而LUMO能级分别为-3.59，-3.62，-3.63，-3.62，-3.61eV。结果表明，引入溴原子和氧原子或烷氧基主要对化合物的HOMO能级影响较大；而它们的LUMO能级影响较小，这是由于其LUMO能级主要由受体单元决定。
实施例4
图3为化合物M1～M5在甲苯溶液(10-5M)中的紫外可见吸收光谱图。由图可知，化合物M1～M5在300-400nm区间的吸收峰主要归属于分子内芳环的π-π*跃迁；在400-500nm间的宽吸收峰为分子内给体单元到受体单元的电荷转移跃迁(ICT)。化合物M1～M5在除氧甲苯溶液(10-5M)和薄膜中的光致发光谱分别如图4和图5所示。显然，化合物M1～M5在甲苯和薄膜中都呈现出双发射峰。其中M1～M5在溶液中的最大发射峰分别510/605，518/605，490/625，510/618，470/593nm；而在薄膜中的发射峰分别是510/660，518/650，532，534，540nm。随着氧原子和烷氧基的插入，化合物M1～M5在甲苯溶液中的发射峰位置红移。
为了验证化合物M1～M5的TADF性能，我们利用瞬态荧光光谱分别测试了它们在除氧甲苯溶液和薄膜下的发射寿命。化合物M1～M5在短波长处的平均发射寿命都在微妙级别，属于延迟荧光的寿命范畴，表明这些化合物利用了反系间窜越的三线态激子，有利于内量子效率的提高；同时它们的发光寿命也不至于过长，有效地防止了非辐射跃迁带来的激子损耗，提高了辐射跃迁常数，进一步提高了材料的发光效率。
实施例5
为了进一步研究这类材料的电致发光性能，我们以化合物M1～M5为发光层掺杂剂，以[(PVK:OXD-7)7:3]为主体材料，通过溶液旋涂的方法，制备电致发光器件。其中化合物M1～M5的掺杂比例为10wt％。具体的器件结构如下：ITO/PEDOT:PPS(40nm)/PVK:OXD-7[7:3]:emitter(10wt％,50nm)/TmPyPB(50nm)/CsF(1.2nm)/Al(120nm)。其中ITO为阳极，PEDOT:PPS为空穴传输层，PVK:OXD-7为主体掺杂材料，emitter为客体发光材料，TmPyPB为电子传输层，CsF/Al为阴极。
图6为化合物M1～M5的电致发光光谱图(EL)。由图可知，它们的EL光谱呈现出两个发射峰。其中，在420nm左右的发射峰来源于主体材料PVK+OXD-7的发光，这表明主客体材料间的能量传递不完全。另一方面，长波长的发射主要来源于发光材料M1～M5的发光，它们的最大发射峰分别为612,614,622,624,614nm。实验结果表明，间隔1个氧原子对材料的发射影响较小；当引入烷氧基链时，其EL发射峰明显红移。基于化合物M1-M5的器件最大亮度分别是706,419,374,251和1055cd/m2。
器件的外量子效率(EQE)随电流密度的变化如图7所示。结果表明，M1～M5的最大外量子效率分别为2.51,2.22,1.22,1.57,3.74％,随着引入氧原子和烷氧基链对体系共轭打断程度的增加，最大外量子效率都出现了下降的趋势，并且在较低的电流密度下，M1～M5从0.1mA/cm2到100mA/cm2的效率滚降分别是81％,87％,80％,83％,83％。
Claims (3)
1.一种基于咔唑-二苯砜蓝光发色团和三苯胺-蒽醌橙红光发色团的双发色团热活性延迟荧光材料，其特征在于：具有M1～M5结构：
2.根据权利要求1所述的热活性延迟荧光材料M1～M5，其特征在于：材料在溶液和固体薄膜中的光致发光呈现出双发射峰。
3.权利要求1所述的热活性延迟荧光材料的应用，其特征在于：作为发光层掺杂剂材料用于溶液加工型有机电致发光器件，其最大外量子效率为3.96％。
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| CN104610958A (zh) * | 2015-02-06 | 2015-05-13 | 东南大学成贤学院 | 基于咔唑和二苯砜的热激活延迟荧光材料及其制备方法 |
| CN109411633A (zh) * | 2018-08-31 | 2019-03-01 | 昆山国显光电有限公司 | 一种有机电致发光器件及其制备方法和显示装置 |
| CN109400590A (zh) * | 2018-11-21 | 2019-03-01 | 苏州大学 | 一种热活化延迟荧光材料及其在有机发光二极管中的应用 |
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