CN112898962A - (C^N)Pt(II)(N-Donor)Cl型多核聚集诱导磷光增强发光材料 - Google Patents
(C^N)Pt(II)(N-Donor)Cl型多核聚集诱导磷光增强发光材料 Download PDFInfo
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Abstract
Description
技术领域
本发明属于有机电致发光材料技术领域,具体涉及一种具有聚集诱导磷光增强(AIPE)特性的(C^N)Pt(II)(N-Donor)Cl型多核聚集诱导磷光增强发光材料。
背景技术
聚集诱导发光材料是近年来的研究热点,该类材料在有机发光二极管、传感及生物标记与示踪等方面都有重要应用。有机发光二极管中发光材料以固态的形式存在,因此聚集诱导发光材料在有机发光二极管领域显示出独特的优势。
目前,传统的荧光聚集诱导发光材料在有机发光二极管中已经广泛应用,与传统荧光发光材料相比表现出一定的优势。但是,其荧光发射的特性决定了器件电致发光效率不高,所以寻找高效聚集诱导发光材料提升有机发光二极管效率非常重要。近年来,具有聚集诱导发光特性的磷光材料也被用于制备有机发光二极管。不同于荧光材料,磷光材料可同时利用单线态和三线态发光,可有效提高有机发光二极管的电致发光效率。遗憾的是,大多数磷光聚集诱导发光材料的电致发光效率还远低于预期,只有个别材料表现出较高的电致发光效率。令人欣喜的是,最近研究表明:(C^N)Pt(II)(N-Donor)Cl型单核配合物不仅表现出聚集诱导磷光增强行为,而且其电致发光效率非常高,甚至优于结构相近的传统Pt(II)配合物磷光材料。因此,它们在有机电致发光领域具有很大的潜力。
虽然(C^N)Pt(II)(N-Donor)Cl型聚集诱导磷光增强配合物在有机电致发光领域表现优异,但是目前报道的这类配合物都仅有一个Pt(II)中心,属于单核配合物磷光分子。研究表明,进入多金属中心开发多核配合磷光分子是优化磷光分子电致发光特性的重要手段。因此,针对这一现状,开发新型多核(C^N)Pt(II)(N-Donor)Cl型聚集诱导磷光增强配合物是优化和提升聚集诱导磷光增强配合物电致发光性能的重要举措,对于实现聚集诱导发光材料在有机电致发光领域的应用具有非常重要的意义。
发明内容
为了克服上述现有技术的缺陷,本发明的目的在于设计合成一类具有多个Pt(II)中心的(C^N)Pt(II)(N-Donor)Cl型多核聚集诱导磷光增强发光材料,解决了聚集诱导磷光增强发光材料电致发光效率低及(C^N)Pt(II)(N-Donor)Cl型聚集诱导磷光增强配合物结构相对单一的问题,表现出磷光聚集诱导发光(AIPE)行为。
为了实现上述目标,本发明采用以下技术方案:
(C^N)Pt(II)(N-Donor)Cl型多核聚集诱导磷光增强发光材料,其结构通式为:
(C^N)Pt(II)(N-Donor)Cl型多核聚集诱导磷光增强发光材料,至少包含如下结构:
本发明的优点:
(C^N)Pt(II)(N-Donor)Cl型多核聚集诱导磷光增强发光材料的溶液中加入不良溶剂,比如水、正己烷、苯基甲苯等不良溶剂,可使磷光发射信号增强,表现出磷光聚集诱导发光(AIPE)行为。
附图说明
图1为前驱体配合物Dimer的合成路线。
图2典型多核配合物合成路线。
图3是PO-ppy-2的聚集诱导发光行为。
图4是PO-ppy-3的聚集诱导发光行为。
图5是PO-pay-2的聚集诱导发光行为。
图6是PO-pay-3的聚集诱导发光行为。
具体实施方式
下面通过实施例,对本发明的技术方案做进一步的详细描述。
(C^N)Pt(II)(N-Donor)Cl型多核聚集诱导磷光增强发光材料,其结构通式为:
N-1的合成:
氮气氛围下,在Schlenk反应管中加入1,3-二溴苯(0.1mol)、吡啶-4-硼酸(0.22mol)和Pd(PPh3)4(0.01mol)加入体积比为2:1的1,4-二氧六环和2M碳酸钠混合溶液,反应体系升至110℃反应16h,反应完成后二氯甲烷萃取,水洗,干燥,浓缩,粗产物用硅胶柱或者薄层色谱提纯,洗脱剂为适量比的二氯甲烷和乙酸乙酯混合溶液。白色固体,产率75%。1H NMR(400MHz,CDCl3):δ(ppm)8.70(d,J=4.0Hz,4H),7.86(s,1H),7.71-7.69(m,2H),7.63-7.59(m,2H),7.50(d,J=6.0Hz,4H)。
N-2的合成:
氮气氛围下,在Schlenk反应管中加入1,3,5-三溴苯(0.2mol)、吡啶-4-硼酸(0.66mol)和Pd(PPh3)4(0.03mol)加入体积比为2:1的1,4-二氧六环和2M碳酸钠混合溶液,反应体系升至110℃反应24h,反应完成后二氯甲烷萃取,水洗,干燥,浓缩,粗产物用硅胶柱或者薄层色谱提纯,洗脱剂为适量比的二氯甲烷和乙酸乙酯混合溶液。白色固体,产率64%。1H NMR(400MHz,CDCl3):δ(ppm)8.75(d,J=5.2Hz,6H),7.92(s,3H),7.61(d,J=6.0Hz,6H)。
N-4的合成:
氮气氛围下,在Schlenk反应管中加入4,4’,4”-三溴三苯胺(0.1mol)、吡啶-4-硼酸(0.33mol)和Pd(PPh3)4(0.015mol)加入体积比为2:1的1,4-二氧六和2M碳酸钠混合溶液,反应体系升至110℃反应24h,反应完成后二氯甲烷萃取,水洗,干燥,浓缩,粗产物用硅胶柱或者薄层色谱提纯,洗脱剂为适量比的二氯甲烷和乙酸乙酯混合溶液。白色固体,产率58%。1H NMR(400MHz,CDCl3):δ(ppm)8.64(d,J=4.4Hz,4H),7.60(d,J=8.4Hz,4H),7.50(d,J=4.4Hz,4H),7.25(d,J=8.4Hz,4H)。
N-6的合成:
氮气氛围下,在Schlenk反应管中加入4,4’-二溴三苯基氧膦(0.1mol)、吡啶-4-硼酸(0.22mol)和Pd(PPh3)4(0.01mol)加入体积比为2:1的1,4-二氧六环和2M碳酸钠混合溶液,反应体系升至110℃反应16h,反应完成后二氯甲烷萃取,水洗,干燥,浓缩,粗产物用硅胶柱或者薄层色谱提纯,洗脱剂为适量比的二氯甲烷和乙酸乙酯混合溶液。白色固体,产率61%。1H NMR(400MHz,CDCl3):δ(ppm)8.70(dd,J=4.4,1.6Hz,4H),7.86-7.81(m,4H),7.76-7.10(m,6H),7.60(td,J=7.4,1.5Hz,1H),7.54-7.50(m,6H);31P NMR(162MHz,CDCl3):δ(ppm)28.27。
N-7的合成:
氮气氛围下,在Schlenk反应管中加入3,6-二溴-N-苯基咔唑(0.2mol)、吡啶-4-硼酸(0.44mol)和Pd(PPh3)4(0.02mol)加入体积比为2:1的1,4-二氧六环和2M碳酸钠混合溶液,反应体系升至110℃反应16h,反应完成后二氯甲烷萃取,水洗,干燥,浓缩,粗产物用硅胶柱或者薄层色谱提纯,洗脱剂为适量比的二氯甲烷和乙酸乙酯混合溶液。白色固体,产率64%。1H NMR(400MHz,CDCl3):δ(ppm)8.69(d,J=5.6Hz,4H),8.50(d,J=1.6Hz,2H),7.47(dd,J=8.4,1.6Hz,2H),7.69-7.65(m,6H),7.62-7.59(m,2H),7.56-7.51(m,3H)。
(C^N)Pt(II)(N-Donor)Cl型多核聚集诱导磷光增强发光材料,至少包含如下结构:
(C^N)Pt(II)(N-Donor)Cl型多核聚集诱导磷光增强发光材料的合成
参照图1,Dimer-ppy的合成:
氮气氛围下,在Schlenk反应管中加入氯亚铂酸钾(0.01mol)和2-苯基吡啶(ppy,0.011mol),然后加入体积比为3:1的乙二醇乙醚和水混合溶液,90℃下反应16h。待反应管冷却至室温后,将反应体系倒入到饱和食盐水中,过滤,用水洗涤三次并收集固体,然后将固体放入真空干燥箱中烘干得到Dimer-ppy,产率65%。
参照图1,Dimer-pay的合成:
氮气氛围下,在Schlenk反应管中加入氯亚铂酸钾(0.02mol)和4-(2-吡啶基胺)三苯(pay,0.022mol),然后加入体积比为3:1的乙二醇乙醚和水混合溶液,90℃下反应16h。待反应管冷却至室温后,将反应体系倒入到饱和食盐水中,过滤,用水洗涤三次并收集固体,然后将固体放入真空干燥箱中烘干得到Dimer-pay,产率60%。
具体的:
参照图2,Ph-pay-2的合成:
氮气氛围下,在反应管中加入Dimer-pay(0.02mol)、N-1(0.02mol)及溶剂为氯仿(15mL)。反应体系在50℃下反应12h,反应完成后直接浓缩,粗产物用硅胶薄层色谱分离纯化,展开剂CH2Cl2:CH3OH=20:1的体系进行分离。黄色固体,产率61%。1H NMR(400MHz,CDCl3):δ(ppm)9.60(d,J=5.4Hz,2H-1),8.88(d,J=6.7Hz,4H-2),7.78-7.69(m,6H),7.52(d,J=7.8Hz,2H),7.36-7.33(m,6H),7.16(t,J=7.8Hz,8H),7.05(d,J=7.6Hz,10H),6.89(t,J=7.3Hz,4H),6.80(dd,J=8.4,2.1Hz,2H),5.98(d,J=2.1Hz,2H);13C NMR(100MHz,CDCl3):δ(ppm)166.80,153.97,151.16,149.35,148.59,147.19,142.29,138.64,137.90,137.66,130.44,129.10,128.57,125.38,124.58,123.99,123.41,123.27,120.64,117.59,117.00.
Ph-pay-3的合成:
氮气氛围下,在反应管中加入Dimer-pay(0.03mol)、N-2(0.02mol)及溶剂为氯仿(20mL)。反应体系在50℃下反应12h,反应完成后直接浓缩,粗产物用硅胶薄层色谱分离纯化,展开剂CH2Cl2:CH3OH=20:1的体系进行分离。黄色固体,产率35%。1H NMR(400MHz,CDCl3):δ(ppm)9.60(d,J=5.2Hz,3H-1),8.98(d,J=6.6Hz,6H-2),7.81(s,3H-3),7.77(t,J=7.8Hz,3H),7.52(d,J=8.1Hz,3H),7.44(d,J=6.7Hz,6H),7.34(d,J=8.5Hz,3H),7.14(t,J=7.8Hz,12H),7.04(d,J=7.5Hz,15H),6.85(t,J=7.3Hz,6H),6.79(dd,J=8.5,2.2Hz,3H),6.05(d,J=2.2Hz,3H);13C NMR(100MHz,CDCl3):δ(ppm)166.78,154.35,151.17,149.32,147.61,147.23,142.26,139.11,138.75,138.10,129.10,126.76,125.25,124.70,124.15,123.49,123.15,120.74,117.67,117.42.
TPA-pay-2的合成:
氮气氛围下,在反应管中加入Dimer-pay(0.02mol)、N-3(0.02mol)及溶剂为氯仿(15mL)。反应体系在50℃下反应12h,反应完成后直接浓缩,粗产物用硅胶薄层色谱分离纯化,展开剂CH2Cl2:CH3OH=20:1的体系进行分离。黄色固体,产率55%。1H NMR(400MHz,CD2Cl2):δ(ppm)9.53(d,J=5.6Hz,2H-1),8.67(d,J=6.8Hz,4H-2),7.79(t,J=7.8Hz,2H),7.58-7.53(m,6H),7.42(t,J=7.8Hz,2H),7.35-7.24(m,14H),7.20(t,J=7.8Hz,8H),7.09-7.03(m,9H),6.95(t,J=7.4Hz,4H),6.77(dd,J=8.8,2.4Hz,2H),5.93(d,J=2.4Hz,2H);13C NMR(100MHz,CD2Cl2):δ(ppm)166.51,152.99,150.40,148.97,148.66,148.22,146.77,145.93,142.53,138.21,137.24,129.45,128.73,127.86.127.68,125.99,125.79,125.10,124.67,123.98,123.28,123.04,121.99,120.20,117.22,115.85.
TPA-pay-3的合成:
氮气氛围下,在反应管中加入Dimer-pay(0.03mol)、N-4(0.02mol)及溶剂为氯仿(20mL)。反应体系在50℃下反应12h,反应完成后直接浓缩,粗产物用硅胶薄层色谱分离纯化,展开剂CH2Cl2:CH3OH=20:1的体系进行分离。黄色固体,产率31%。1H NMR(400MHz,CDCl3):δ(ppm)9.61(d,J=5.2Hz,3H-1),8.77(d,J=6.0Hz,6H-2),7.76(t,J=7.6Hz,3H),7.57(d,J=8.4Hz,6H),7,.51(d,J=8.0Hz,3H),7.35(t,J=8.4Hz,9H),7.28(d,J=6.4Hz,6H),7.19(t,J=7.6Hz,12H),7.06(d,J=8.0Hz,15H),6.95(t,J=7.0Hz,6H),6.81(d,J=7.6Hz,3H),5.99(s,3H).13C NMR(100MHz,CDCl3):δ(ppm)166.80,153.64,151.15,149.33,148.40,148.33,147.26,142.31,138.59,137.95,131.39,129.11,128.40,126.10,125.41,124.87,124.53,123.26,122.67,120.64,117.57,116.94.
PO-ppy-2的合成:
氮气氛围下,在反应管中加入Dimer-ppy(0.02mol)、N-5(0.02mol)及溶剂为氯仿(15mL)。反应体系在50℃下反应12h,反应完成后直接浓缩,粗产物用硅胶薄层色谱分离纯化,展开剂CH2Cl2:CH3OH=20:1的体系进行分离。黄色固体,产率57%。1H NMR(400MHz,CDCl3):δ(ppm)9.70(d,J=5.8Hz,2H-1),9.08(d,J=6.8Hz,4H-2),7.93-7.88(m,4H),7.85-7.82(m,6H),7.78-7.73(m,2H),7.68-7.62(m,7H),7.58-7.54(m,2H),7.50(d,J=7.6Hz,2H),7.18-7.10(m,4H),7.02-6.99(m,2H),6.45(d,J=7.6Hz,2H);31P NMR(162MHz,CDCl3):δ(ppm)27.66.
PO-ppy-3的合成:
氮气氛围下,在反应管中加入Dimer-ppy(0.03mol)、N-6(0.02mol)及溶剂为氯仿(20mL)。反应体系在50℃下反应12h,反应完成后直接浓缩,粗产物用硅胶薄层色谱分离纯化,展开剂CH2Cl2:CH3OH=20:1的体系进行分离。黄色固体,产率38%。1H NMR(400MHz,CDCl3):δ(ppm)9.71(d,J=4.8Hz,3H-1),9.10(dd,J=5.4,1.4Hz,6H-2),7.98-7.93(m,6H),7.90-7.86(m,6H),7.84-7.82(m,3H),7.69-7.65(m,9H),7.52-7.50(m,3H),7.19-7.11(m,6H),7.01(td,J=7.4,1.3Hz,3H),6.46(d,J=7.6Hz,3H);31P NMR(162MHz,CDCl3):δ(ppm)26.89.
PO-pay-2的合成:
氮气氛围下,在反应管中加入Dimer-pay(0.02mol)、N-5(0.02mol)及溶剂为氯仿(15mL)。反应体系在50℃下反应12h,反应完成后直接浓缩,粗产物用硅胶薄层色谱分离纯化,展开剂CH2Cl2:CH3OH=20:1的体系进行分离。黄色固体,产率55%。1H NMR(400MHz,CDCl3):δ(ppm)9.58(d,J=5.6Hz,2H-1),8.85(d,J=6.8Hz,4H-2),7.92-7.87(m,4H),7.80-7.74(m,4H),7.69-7.64(m,5H),7.60-7.55(m,2H),7.51(d,J=8.4Hz,2H),7.34-7.29(m,6H),7.16(t,J=7.8Hz,8H),7.04(d,J=7.6Hz,10H),6.92(t,J=7.4Hz,4H),6.80(dd,J=8.4,2.0Hz,2H),5.93(d,J=2.0Hz,2H);31P NMR(162MHz,CDCl3):δ(ppm)27.77.
PO-pay-3的合成:
氮气氛围下,在反应管中加入Dimer-pay(0.03mol)、N-6(0.02mol)及溶剂为氯仿(20mL)。反应体系在50℃下反应12h,反应完成后直接浓缩,粗产物用硅胶薄层色谱分离纯化,展开剂CH2Cl2:CH3OH=20:1的体系进行分离。黄色固体,产率36%。1H NMR(400MHz,CDCl3):δ(ppm)9.58(d,J=5.6Hz,3H-1),8.86(d,J=6.8Hz,6H-2),7.98-7.93(m,6H),7.78-7.71(m,9H),7.51(d,J=8.0Hz,3H),7.33-7.30(m,9H),7.16(t,J=7.8Hz,12H),7.07-7.03(m,15H),6.91(t,J=7.4Hz,6H),6.79(dd,J=8.4,2.4Hz,3H),5.94(d,J=2.4Hz,3H);31P NMR(162MHz,CDCl3):δ(ppm)27.07.
CAZ-pay-2的合成:
氮气氛围下,在反应管中加入Dimer-pay(0.02mol)、N-7(0.02mol)及溶剂为氯仿(15mL)。反应体系在50℃下反应12h,反应完成后直接浓缩,粗产物用硅胶薄层色谱分离纯化,展开剂CH2Cl2:CH3OH=20:1的体系进行分离。黄色固体,产率57%。1H NMR(400MHz,CDCl3):δ(ppm)9.62(d,J=4.8Hz,2H-1),8.79(d,J=6.8Hz,4H-2),8.47(d,J=1.6Hz,2H),7.78-7.61(m,9H),7.58(d,J=8.4Hz,2H),7.51(d,J=8.0Hz,2H),7.45(d,J=6.8Hz,4H),7.33(d,J=8.4Hz,2H),7.17(t,J=7.8Hz,8H),7.07-7.05(m,10H),6.91(t,J=7.2Hz,4H),6.82(dd,J=8.4,2.4Hz,2H),6.01(d,J=2.4Hz,2H);13C NMR(100MHz,CDCl3):δ(ppm)166.85,153.51,151.14,149.88,149.37,147.19,142.58,142.41,138.53,137.81,136.51,130.35,129.11,128.76,128.60,127.08,125.74,125,47,124.49,124.04,123.92,123.33,123.12,120.58,119.28,117.53,116.70,111.17.
CAZ-pay-3的合成:
氮气氛围下,在反应管中加入Dimer-pay(0.03mol)、N-8(0.02mol)及溶剂为氯仿(20mL)。反应体系在50℃下反应12h,反应完成后直接浓缩,粗产物用硅胶薄层色谱分离纯化,展开剂CH2Cl2:CH3OH=20:1的体系进行分离。黄色固体,产率34%。1H NMR(400MHz,CDCl3):δ(ppm)9.62(d,J=6.0Hz,3H-1),8.91(d,J=6.8Hz,2H-2),8.82(d,J=6.8Hz,4H-3),8.49(d,J=1.2Hz,2H),7.89(d,J=4.8Hz,4H),7.77(t,J=7.2Hz,5H),7.68(d,J=8.8Hz,2H),7.53(t,J=7.4Hz,3H),7.46(d,J=6.8Hz,3H),7.42(d,J=6.8Hz,2H),7.35(t,J=7.9Hz,4H),7.22(d,J=7.5Hz,4H),7.17(t,J=7.8Hz,8H),7.11-7.05(m,14H),7.00(t,J=7.3Hz,3H),6.91(t,J=7.3Hz,4H),6.84-6.81(m,3H),6.04-6.01(m,3H);13C NMR(100MHz,CDCl3):δ(ppm)166.84,154.04,153.60,151.15,149.66,149.36,147.30,147.21,142.39,142.13,138.56,137.85,129.35,129.16,129.11,127.73,125.99,125.47,124.52,124.28,124.04,123.30,123.16,120.70,120.60,119.44,117.63,117.56,117.07,116.77,111.09.
聚集诱导磷光增强表征
选取多核配合物PO-ppy-2、PO-ppy-3、PO-pay-2及PO-pay-3为研究对象。将多核配合物溶于四氢呋喃,配制10-3M的溶液备用。以水与四氢呋喃制备水的体积百分数分别为10%、30%、50%、60%、70%、80%及90%的7种混合溶剂。取任一种混合溶剂2mL加入具塞荧光比色皿,然后用微量注射器取配合物溶液50μL加入盛有混合物溶剂的荧光比色皿并充分混合。静置2min后,测试样品发射光谱,得到不同水体积比条件下的发射光谱(如图3-6)。实验结果表明:在一定范围内随着溶剂中水体积分数增加,多核配合物的磷光发射强度明显增强,表现出明显的聚集诱导磷光增强行为。
以上内容仅为说明本发明的技术思想,不能以此限定本发明的保护范围,凡是按照本发明提出的技术思想,在技术方案基础上所做的任何改动,均落入本发明权利要求书的保护范围之内。
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