CN115490631B - 基于双氰基非那烯近红外热激活延迟荧光发光材料与应用 - Google Patents

基于双氰基非那烯近红外热激活延迟荧光发光材料与应用 Download PDF

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CN115490631B
CN115490631B CN202211232425.6A CN202211232425A CN115490631B CN 115490631 B CN115490631 B CN 115490631B CN 202211232425 A CN202211232425 A CN 202211232425A CN 115490631 B CN115490631 B CN 115490631B
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luminescent material
dicyanophenalene
near infrared
tadf
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刘煜
马斌
丁振民
朱卫国
周忠鑫
张诗玥
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Changzhou University
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Abstract

本发明属于发光与显示技术领域，具体涉及一类基于双氰基非那烯近红外热激活延迟荧光(TADF)发光材料与应用。这类发光材料以共轭平面性好、吸电子能力强的双氰基非那烯为电子受体(A)单元，以咔唑、吖啶、萘、吩恶嗪、吩噻嗪、三苯胺或二苯基硅杂吖啶为给体(D)单元，构筑具有D‑A‑D分子结构、并在D和A单元之间有较大邻位扭曲效应，较好HOMO和LUMO分离程度和较小S1‑T1能量分裂(ΔEST)的TADF发光材料。以该发光材料为发光层掺杂制备了有机电致发光器件，当器件最大发射峰位于908nm近红外区，其对应的最大外量子效率为0.139％，在有机电致发光显示器和生物成像等领域具有广泛的应用。

Description

基于双氰基非那烯近红外热激活延迟荧光发光材料与应用
技术领域
本发明属于发光与显示技术领域，特别涉及一种基于双氰基非那烯近红外热激活延迟荧光(TADF)发光材料与应用。
背景技术
近红外有机电致发光器件(NIR-OLEDs)可广泛应用于生物成像、通信、夜视、传感、医疗和能源等领域，近年来受到了研究者的广泛重视。到目前为止，有机NIR-OLEDs发光材料主要包括过渡金属配位化合物、低带隙聚合物、有机染料和有机D-A型小分子荧光材料。目前基于过渡金属配合物的磷光近红外发光材料的外量子效率达到了24％，但是由于其长寿命三重态激子淬灭效应，在高电流密度下存在稳定性差和效率滚降严重等缺点，严重制约了其实际应用。因此，开发结构简单、易合成，价格低廉的有机小分子近红外发光材料显得尤为迫切。
2012年，Adachi团队获得了具有较小单线态(S0)-三重态(T1)能量分裂(ΔEST)的纯有机小分子热活性延迟荧光(TADF)发光材料，利用反向系间穿越(RISC)，实现了单线态和三线态激子的充分利用以及高效的发光。目前，基于有机TADF材料已实现高效的全色发光显示，但是，基于发光波长超过700nm的近红外有机TADF材料报道较少。
为了实现有机发光材料的高效近红外发射，人们越来越关注具有TADF性能的近红外发光材料的开发及其电致发光器件的制备，如2019年，布朗斯坦等人报道了一种基于苊的近红外TADF荧光发光材料CAT-1，获得了最大发射峰为904nm和对应的最大外量子效率(EQE)为0.019％的近红外电致发光器件(J.Am.Chem.Soc.2019,141,18390–18394)；2020年，廖良生课题组报道的一种基于苊为受体的近红外TADF发光材料DCPA-BBPA，获得了在最大发射峰为916nm和最大EQE为0.07％的近红外电致发光器件(Angew.Chem.Int.Ed.2020,59,21578-21584)；同年，乔娟课题组开发了一种苊为受体的近红外TADF发光材料TPAAZ，获得了在最大发射峰为1010nm和最大EQE为0.003％的近红外电致发光器件。
显然，尽管有机近红外TADF材料在过去几年中取得了一定的进展，但发光效率由于受到能隙定律的限制，材料的发光效率仍然偏低，仍有很多科学问题亟需解决，具体是：1、构筑TADF材料的受体单元严重短缺，目前常用的受体单元通常为二苯并吩嗪、吡嗪、庚嗪和喹喔啉等结构；2.近红外发光材料的效率受到能隙定律的限制，材料的发光效率通常随着发光波长的增加而快速降低，这就导致有机近红外发光材料很难获得高效发光。
发明内容
为了进一步构筑新型近红外TADF材料的受体单元，本发明设计并构筑了一类新型的平面性好、强吸电子能力的双氰基非那烯结构单元，并在外围引入对称性的两个咔唑、吖啶、萘、吩恶嗪、吩噻嗪、三苯胺或二苯基硅杂吖啶等强给电子单元，获得了一类具有扭曲结构的高效近红外TADF荧光材料。
本发明获得高效的长波长近红外发光材料，分子的设计依据以下设计原则：1)选择相匹配的给-受体单元进行有效组合，获得分离的HOMO和LUMO电子结构，促使分子具有电荷转移激发态(CT)达到近红外发射；2)选择具有刚性结构的分子，利用其较大位阻来抑制非辐射跃迁，提高荧光发光效率等；3)选择合适的给电子单元和吸电子单元的嫁接方式来调控材料分子的HOMO和LUMO在空间的重叠程度，提高辐射跃迁速率；4)通过有效提升反向系间穿越(RISC)，实现了单线态和三线态激子的充分利用以及高效的发光，获得具有TADF性能的材料。本发明对于探索扩展不同受体的近红外TADF材料具有重要的意义。
本发明所涉及的化合物的结构通式如下所示：
其中，D是咔唑、3,6-二甲氧基咔唑、三芳胺、N,N-双(4-甲氧基)苯胺、吖啶、吩恶嗪、吩噻嗪、N,N-双(4-萘基)苯胺、N,N-双(4-联苯基)苯胺或二苯基硅杂吖啶单元。
D基代表型结构如下式所示：
本发明所涉及到的代表性双氰基非那烯衍生物(1-9)如下所示：
优选的双氰基非那烯衍生物TG-1和TG-2D的分子结构式如下所示：
本发明还提供了所述的双氰基非那烯衍生物近红外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，用于有机电致发光二极管。其中，发光层通过溶液加工方法实现。
一种近红外OLEDs溶液加工器件，器件结构为:ITO/PEDOT:PSS/PVK/CBP:NIR-TADF-emitter/DPEPO/TmPyPB/LiF/Al。
有益效果：本发明以平面刚性好、吸电子能力强的双氰基非那烯为受体(A)单元，以强给电子(D)单元咔唑、3,6-二甲氧基咔唑、三芳胺、N,N-双(4-甲氧基)苯胺、吖啶、吩恶嗪、吩噻嗪、N,N-双(4-萘基)苯胺、N,N-双(4-联苯基)苯胺或二苯基硅杂吖啶单元，构筑的D-A-D结构的具有TADF性质的荧光发光材料，构筑的分子结构未见文献报道；这类材料的分子结构简单，易合成，光致发光光谱的波长超过了800nm近红外区，构筑的电致发光器件的最大波长达到了908nm的近红外区，器件的外量子效率达到了0.139％，具有潜在的应用前景。
附图说明：
【图1】为本发明实施例1制得的化合物TG-1和TG-2在甲苯溶液中的紫外可见光吸收光谱图。
【图2】为本发明实施例1制得的化合物TG-1和TG-2在甲苯溶液中的光致发光光谱图。
【图3】为本发明实施例1制得的化合物TG-1和TG-2在10％掺杂CBP薄膜中的光致发光光谱。
【图4】为本发明实施例1制得的化合物TG-1分别在正己烷、四氯化碳、甲苯和乙醚溶液中的光致发光光谱图。
【图5】为本发明实施例1制得的化合物TG-2分别在正己烷、四氯化碳、甲苯和乙醚溶液中的光致发光光谱图。
【图6】为本发明实施例1制得的化合物TG-1在10％掺杂CBP薄膜中的瞬时荧光寿命谱图
【图7】为本发明实施例1制得的化合物TG-1在10％掺杂CBP薄膜中的延迟荧光寿命谱图
【图8】为本发明实施例1制得的化合物TG-2在10％掺杂CBP薄膜中的瞬时荧光寿命谱图
【图9】为本发明实施例1制得的化合物TG-2在10％掺杂CBP薄膜中的延迟荧光寿命谱图
【图10】为本发明实施例1制得的化合物TG-1在不同掺杂浓度下的电致发光光谱图。
【图11】为本发明实施例1制得的化合物TG-2在不同掺杂浓度下的电致发光光谱图。
【图12】为本发明实施例1制得的化合物TG-1在不同掺杂浓度下的外量子效率图。
【图13】为本发明实施例1制得的化合物TG-2在不同掺杂浓度下的外量子效率图。
具体实施方式
以下具体实施案例旨在对本发明做进一步说明，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
基于氰基非那烯结构单元的近红外TADF材料TG-1和TG-2合成路线如下所示：
化合物SM1的合成
在200mL单口瓶中加入苊(10.0g，64.90mmol)，加入溶剂DMF(100mL)，保持在0℃下避光加入N-溴代琥珀酰亚胺(28.88g，162.25mmol)，室温下避光搅拌过夜。过滤得到粗产物，并通过从乙醇中重结晶纯化，得到5.05g SM1，为米色晶体，收率25％。1H NMR(500MHz,CDCl3)δ7.79(d,J＝7.4Hz,2H),7.09(d,J＝7.4Hz,2H).
化合物SM2的合成
在500mL单口瓶中加入化合物SM1(2.00g,6.4mmol)、300mL醋酸酐，保持温度在110℃直至化合物SM1完全溶解，分多次将三氧化铬(5.00g，49.70mmol)加入单口瓶中，升温至160℃保持30分钟。待反应结束后，冷却至室温，加入大量冰水，4mL盐酸，抽滤，得到棕黄色固体粗产物，烘干后将粗产物通过醋酸酐纯化，得到2.00g SM2，为黄褐色粉末，产率82％。1H NMR(500MHz,CDCl3)δ＝8.29–8.25(d,J＝7.6,2H),7.95–7.91(d,J＝7.6,2H)
化合物SM3的合成
将化合物SM2(2.00g,5.80mmol)、(4-(二苯基氨基)苯基)硼酸(3.47g,12.00mmol)和Pd(PPh3)4(0.46g,0.40mmol)在氮气氛下将其溶解在200mL THF中。在50℃搅拌所得混合物10分钟后，加入40mL脱气的2M K2CO3水溶液，然后回流过夜。将反应混合物冷却至室温并在真空条件下除去THF。将固体残余物溶解在100mL二氯甲烷中并用水(3×100mL)洗涤。分离有机层并用无水Na2SO4干燥并通过旋转蒸发浓缩。使用石油醚/二氯甲烷(1/3)作为洗脱剂，通过柱色谱法(硅胶)纯剩余固体，得到深红色固体2.20g，产率75％。1H NMR(500MHz,CDCl3)δ＝8.22–8.14(d,J＝7.3,2H),7.84–7.77(d,J＝7.3,2H),7.30–7.15(m,18H),7.08–7.04(t,J＝7.2,4H),6.92–6.83(m,8H).
化合物SM4的合成
将化合物SM3(1.34g,2.00mmol)、丙二腈(264mg,4mmol)和50mL四氢呋喃溶液加入100mL单口瓶中，混合物溶液加热至90℃回流4h。待反应结束后，冷却至室温，减压旋除四氢呋喃，剩下的反应物固体乙醇洗涤(100mL)去除未反应的丙二腈、干燥、减压蒸馏除去剩余溶剂，剩余物用石油醚/二氯甲烷(1/1)为洗脱剂柱层析分离得到深绿色固体1.00g，产率70％。1H NMR(500MHz,CDCl3)δ＝8.22–8.14(d,J＝7.3,2H),7.84–7.77(d,J＝7.3,2H),7.30–7.15(m,18H),7.08–7.04(t,J＝7.2,4H),6.92–6.83(m,8H).
化合物TG-1的合成
将化合物SM4(1.0g,1.39mmol)、碳酸钾(100mg,13.9mmol)和100mL四氢呋喃溶液加入200mL单口瓶中，混合物溶液加热至90℃回流1h。待反应结束后，冷却至室温，减压旋除四氢呋喃反应液，用二氯甲烷(3×50mL)萃取，收集的有机层依次通过水洗(100mL)、干燥、减压蒸馏除去溶剂，剩余物用石油醚/二氯甲烷(1/2)为洗脱剂柱层析分离得到墨绿色固体600mg，产率60％。1HNMR(400MHz,CDCl3)δ＝8.73–8.66(d,J＝7.8,1H),8.36–8.29(d,J＝7.8,1H),7.86–7.80(d,J＝7.9,1H),7.73–7.68(d,J＝7.8,1H),7.24–7.15(ddd,J＝8.8,7.2,1.8,8H),7.11–6.98(m,12H),6.94–6.86(dq,J＝9.4,2.8,4H),6.82–6.74(m,4H).
化合物SM5的合成
将化合物SM2(2.00g,5.80mmol)、(4-(二联苯基氨基)苯基)硼酸(5.30g,12.00mmol)和Pd(PPh3)4(0.46g,0.40mmol)在氮气氛下将其溶解在200mL THF中。在50℃搅拌所得混合物10分钟后，加入40mL脱气的2M K2CO3水溶液，然后回流过夜。将反应混合物冷却至室温并在真空条件下除去THF。将固体残余物溶解在100mL二氯甲烷中并用水(3×100mL)洗涤。分离有机层并用无水Na2SO4干燥并通过旋转蒸发浓缩。使用石油醚/二氯甲烷(1/3)作为洗脱剂，通过柱色谱法(硅胶)纯剩余固体，得到深红色固体2.06g，产率36％。1HNMR(400MHz,CDCl3)δ＝8.25–8.19(d,J＝7.2,1H),7.88–7.81(d,J＝7.3,1H),7.58–7.47(dd,J＝23.9,7.9,8H),7.44–7.30(m,10H),7.06–6.94(q,J＝8.4,4H).
化合物SM6的合成
将化合物SM5(1.00g,1.03mmol)、丙二腈(132mg,2mmol)和50mL四氢呋喃溶液加入100mL单口瓶中，混合物溶液加热至90℃回流4h。待反应结束后，冷却至室温，减压旋除四氢呋喃，剩下的反应物固体乙醇洗涤(100mL)去除未反应的丙二腈、干燥、减压蒸馏除去剩余溶剂，剩余物用石油醚/二氯甲烷(1/1)为洗脱剂柱层析分离得到深绿色固体0.66g，产率63％。1H NMR(400MHz,CDCl3)δ＝8.77–8.57(d,J＝7.6,1H),8.27–8.18(d,J＝7.3,1H),7.92–7.81(t,J＝6.8,2H),7.59–7.46(dd,J＝22.6,7.9,17H),7.43–7.37(t,J＝7.5,9H),7.36–7.29(m,14H),7.05–6.94(m,9H).
化合物TG-2的合成
将化合物SM6(0.66g,0.65mmol)、碳酸钾(46.80mg,6.5mmol)和100mL四氢呋喃溶液加入200mL单口瓶中，混合物溶液加热至90℃回流1h。待反应结束后，冷却至室温，减压旋除四氢呋喃反应液，用二氯甲烷(3×50mL)萃取，收集的有机层依次通过水洗(100mL)、干燥、减压蒸馏除去溶剂，剩余物用石油醚/二氯甲烷(1/2)为洗脱剂柱层析分离得到墨绿色固体0.35mg，产率53％。1H NMR(400MHz,CDCl3)δ＝8.86–8.79(d,J＝7.9,1H),8.48–8.36(d,J＝7.8,1H),7.97–7.89(d,J＝7.9,1H),7.85–7.77(d,J＝7.8,1H),7.60–7.47(ddt,J＝16.7,6.7,1.6,16H),7.45–7.37(dd,J＝8.3,6.5,9H),7.36–7.27(m,11H),7.10–6.97(m,7H).
实施例2
将化合物TG-1和TG-2分别溶解在甲苯溶液中配成10-5M溶液，测试其溶液的紫外可见吸收光谱。由图1可知，化合物TG-1和TG-2在溶液中的紫外可见吸收光谱大致有两种吸收峰：两种化合物在320nm左右的吸收带归因于π-π跃迁，395-476nm左右的吸收带是CT+LE态，600nm左右的吸收带归因于分子内电荷转移(ICT)。
实施例3
实施例1中的化合物TG-1和TG-2的光致发光性能测试。将化合物TG-1和TG-2溶解在甲苯中配置成10-5M溶液，测试其溶液的光致发光光谱，如图2所示，在光激发下，所有化合物都在近红外区域。其中化合物TG-1的最大发射峰为802nm，化合物TG-2的发射峰为826nm，完美实现了近红外的要求。
实施例4
将实施例1的化合物TG-1和TG-2分别掺杂在CBP中，测试其10％wtCBP掺杂薄膜的光致发光光谱。由图3可知，在10％CBP掺杂薄膜中化合物TG-1和TG-2的发射峰分别位于844nm和885nm，属于近红外发射。
实施例5
实施例1中的化合物TG-1和TG-2分别在不同溶液中的光致发光性能测试。将化合物TG-1和TG-2分别溶解在正己烷、四氯化碳、甲苯和乙醚溶液中，测试其不同溶液的光致发光光谱，如图4和图5所示。由图可知，在光激发下，化合物的发射波长随着溶剂极性的增加呈现出一定的红移，说明这类化合物具有很强的分子内电荷转移能力。
实施例6
将实施例1的化合物TG-1掺杂在CBP中，测试其10％wtCBP掺杂薄膜的瞬时寿命谱图，如图6所示。根据拟合测得短寿命为1.7ns。
实施例7
将实施例1的化合物TG-1掺杂在CBP中，测试其10％wtCBP掺杂薄膜的延迟寿命谱图，如图7所示。根据拟合测得长寿命为6.06μs，微秒级的寿命证明了TG-1是TADF材料。
实施例8
将实施例1的化合物TG-2掺杂在CBP中，测试其10％wtCBP掺杂薄膜的瞬时寿命谱图，如图8所示。根据拟合测得短寿命为1.9ns。
实施例9
将实施例1的化合物TG-2掺杂在CBP中，测试其10％wtCBP掺杂薄膜的延迟寿命谱图。如图9所示。根据拟合测得长寿命为4.4μs，微秒级的寿命证明了TG-2是TADF材料。
实施例10
实施例1中的化合物TG-1和TG-2的不同掺杂浓度分别在有机电致发光器件中的应用。以化合物TG-1和TG-2分别作为器件发光层的掺杂材料，制备结构为ITO/PEDOT:PSS(40nm)/PVK(10nm)/CBP:TG-1 or TG-2(6wt％，8wt％，10wt％，20wt％，30wt％，40wt％，30nm)/DPEPO(9nm)/TmPyPB(45nm)/LiF(1.2nm)/Al(120nm)的有机电致发光二极管。其中，PEDOT:PSS为空穴注入层，PVK为空穴传输层，CBP为发光层主体材料，TG-1或者TG-2为发光层客体材料，DPEPO为空穴阻挡层，TmPyPB为电子传输层，Liq/Al为阴极。
图10是化合物TG-1的电致发光光谱(EL)图，当掺杂浓度分别为6wt％，8wt％10wt％，20wt％，30wt％和40wt％,其对应的最大发射峰分别位于822nm，826nm，832nm，846nm，866nm和875nm；
图11是TG-1不同掺杂浓度(6wt％，8wt％，10wt％，20wt％，30wt％和40wt％)对应的外量子效率(EQE)图，其对应的EQE分别为0.164％，0.151％，0.137％，0.126％，0.118％和0.113％。
图12是化合物TG-2的电致发光光谱(EL)图，当掺杂浓度分别为6wt％，8wt％，10wt％，20wt％，30wt％和40wt％,其对应的最大发射峰分别位于824nm，831nm,839nm，871nm，881nm和908nm；
图13是不同TG-2掺杂浓度(6wt％，8wt％，10wt％，20wt％，30wt％和40wt％)对应的外量子效率(EQE)图，其对应的EQE分别为0.192％，0.183％，0.175％，0.159％，0.147％和0.139％。
尽管结合了优选实施例对本发明进行了说明，但本发明并不局限于上述实施例，应当理解所附权利要求概括了本发明的范围。在本发明构思的指导下，本领域的技术人员应当意识到，对本发明的各实施例方案所进行的一定的改变，都将被本发明的权利要求书的精神和范围所覆盖。

Claims (5)

1.一种基于双氰基非那烯近红外热活性延迟荧光发光材料，其特征在于，所述荧光发光材料结构式如下所示，
。
2.一种根据权利要求1所述的基于双氰基非那烯近红外热活性延迟荧光发光材料的应用，其特征在于，所述荧光发光材料用于制备有机电致发光器件。
3.根据权利要求2所述的基于双氰基非那烯近红外热活性延迟荧光发光材料的应用，其特征在于，所述荧光发光材料作为有机电致发光器件的发光层。
4.根据权利要求3所述的基于双氰基非那烯近红外热活性延迟荧光发光材料的应用，其特征在于，所述发光层通过溶液或全蒸镀的加工方法实现。
5.一种近红外OLEDs溶液加工器件，其特征在于，所述器件结构为：ITO/PEDOT:PSS /PVK/CBP:TG-1 or TG-2/DPEPO/TmPyPB /LiF /Al，其中，TG-1 or TG-2的结构如权利要求1荧光发光材料结构式所示。
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