CN115246861A - 一种主配体含吲哚并[3,2,1-jk]咔唑衍生物的铱配合物及其应用 - Google Patents
一种主配体含吲哚并[3,2,1-jk]咔唑衍生物的铱配合物及其应用 Download PDFInfo
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Abstract
本发明属于电致发光材料技术领域，涉及一类主配体含有吲哚并[3,2,1‑jk]咔唑及其衍生物的新型铱配合物。本发明将吲哚并[3,2,1‑jk]咔唑及其衍生物引入主配体结构，增加配体和配合物刚性，并实现空间位阻，减少分子堆积，抑制分子的非辐射跃迁过程。本发明中所述铱配合物具有很高的光致发光量子产率以及短激发态寿命。利用本发明所述铱配合物制备的器件性能表现优良，具有高外量子效率、低启动电压及低效率滚降，其在OLED显示与照明领域具有潜在的应用价值。
Description
技术领域
本发明涉及有机电致发光器件(OLED)技术领域，尤其涉及一类主配体含吲哚并[3,2,1-jk]咔唑及其衍生物的铱配合物及其作为发光材料在有机电致发光器件中的应用。
背景技术
OLED的电光转换技术在平板显示和照明领域有着广泛的应用。发光材料是OLED的核心部分，尤其是磷光金属配合物，具有很高的光致发光量子效率和良好的器件性能三价铱配合物具有化学结构易于修饰、光物理性质控制灵活、发光效率高、激发寿命低等优点。值得注意的是，基于杂配体的铱配合物是研究最多的配合物，因为铱配合物的颜色和性质可以通过多种环金属化主配体和辅助配体的组合来调节。然而，为了满足照明和显示应用，OLED具有良好的色纯度和窄光带，高电致发光效率和低效率关断仍然是需要的。
咔唑基是一类具有高空穴传输能力和三重态能量的优良发色团，其衍生物已广泛应用于空穴传输材料、基质材料和发光材料中。咔唑类化合物具有多个活性反应位点，通过与功能单元结合形成发光材料和磷光配合物的有机配体，易于修饰。此外，咔唑单元上不同位置的给电子能力会影响发光材料的能级，因此不同取代位置的功能化将有效地调节配合物的发光颜色和发光效率。其中，含吲哚[3,2,1-jk]咔唑单元的铱配合物配体具有较高的空穴传输能力、较窄的发光带和良好的器件性能，近年来受到了广泛的关注。
发明内容
本发明目的在于针对现有技术不足，设计了一类主配体含有吲哚[3,2,1-jk]咔唑及其衍生物的新型铱配合物，并将该材料应用于有机电致发光器件中，为OLED器件提供了一类新型高效发光材料。
本发明具体技术方案如下：
一种主配体含有吲哚[3,2,1-jk]咔唑及其衍生物的铱配合物，其结构通式如下：
其中用于配位的基团R1代表取代或非取代的芳杂环基；
其中R2、R3相同或者不同，独立地选自烷基，优选C1-C10的烷基；
其中X1、X2相同或者不同，代表C或N。
优选的，所述的铱配合物通式中R1代表任意位被H、C1-C10的烷基、C1-C10的烷氧基、卤素、被一个或多个相同或不同卤素取代的C1-C10的卤代烷基、羟基、氨基、硝基中的一种或几种取代的吡啶基、嘧啶基、异喹啉基、喹唑啉基、吡啶并嘧啶基、噻吩并嘧啶基、呋喃并嘧啶基。
优选的，所述的铱配合物通式中R2，R3选自甲基、乙基、丙基、异丙基、叔丁基、异丁基和异戊基。
进一步优选地，所述的铱配合物通式中R1代表任意位被H、C1-C6的烷基、C1-C6的烷氧基、卤素、被一个或多个相同或不同卤素取代的C1-C6的卤代烷基、羟基、氨基、硝基中的一种或几种取代的：
进一步优选的，R1代表任意位被H、C1-C6的烷基、C1-C6的烷氧基、-CF3、-CCl3、-CBr3、-CH2CF3、-CH2CCl3、-CH2CBr3、卤素、羟基、氨基、硝基中的一种或几种取代的：
优选的，所述铱配合物选自如下结构：
本发明所述的铱配合物可采用常规的方法制备，例如，将主配体和IrCl3以2:1的比例在乙氧基乙醇和水的混合溶液中回流2小时，冷却过滤得到铱的氯桥配合物；然后铱的氯桥配合物和相应结构的β-二酮类辅助配体在乙氧基乙醇中回流2个小时得到铱配合物的粗产物，柱层析得到纯品，并进一步在真空条件下升华提纯得到满足制备器件要求的发光材料。
本发明的另一目的在于提供本发明所述铱配合物作为发光材料在在制备有机电致发光器件中的应用。
本发明所述铱配合物可以用于制备有机电致发光器件，例如，有机电致发光器件包括基片、阳极、空穴注入材料、空穴传输层、有机发光层、电子传输层、电子注入材料和阴极。基片为玻璃，阳极为氧化铟锡(ITO)，空穴注入层为2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(HAT-CN)，空穴层采用4,4'-环己基二[N,N-二(4-甲基苯基)苯胺(TAPC)，电子传输层采用1,3,5-三[(3-吡啶基)-3-苯基]苯(TmPyPb)，电子注入材料为LiF，阴极为金属Al；有机发光层包括主体材料和发光材料，所述主体材料是2，6-双((9H-咔唑-9-基)-3,1-亚苯基)吡啶(2,6DCzPPy)，发光材料为本发明所述铱配合物。
本发明的有益效果：本发明提供的吲哚[3,2,1-jk]咔唑及其衍生物对铱配合物有调控材料发光颜色和电子传输性能，增加材料稳定性，提升器件效率，降低效率滚降的效果。本发明所述铱配合物本发明中所述铱配合物具有较高的光致发光量子产率以及短激发态寿命。利用本发明所述铱配合物制备的器件性能表现优良，具有高外量子效率、低启动电压及低效率滚降，其在OLED照明与显示领域具有潜在的应用价值。
附图说明
图1为本发明中铱配合物Ir01的吸收光谱(图1a)和发射光谱(图1b)及其OLED的亮度-电压-电流密度曲线(图1c)和外量子效率-亮度曲线(图1d)。
图2为本发明中铱配合物Ir05的吸收光谱(图2a)和发射光谱(图2b)及其OLED的亮度-电压-电流密度曲线(图2c)和外量子效率-亮度曲线(图2d)。
具体实施方式
在本发明中所使用的术语，除非另有说明，一般具有本领域普通技术人员通常理解的含义。下面结合具体实施例并参照数据进一步详细描述本发明。应理解，该实施例只是为了举例说明本发明，而非以任何方式限制本发明的范围。
在以下实施例中，未详细描述的各种过程和方法是本领域中公知的常规方法。
实施例1制备本发明中的铱配合物
制备上述路线中化合物L1-1：分别称量5.00g(30mmol)咔唑，4mL(36mmol)邻氟溴苯，11.70g(36mmol)碳酸铯，50mL DMF于500mL的三口瓶中，抽真空并在160℃下搅拌过夜。并取样点板，监测咔唑是否反应完全。如没有反应完全就补加10％eqv的邻氟溴苯继续反应，如反应完全则使反应降至室温，然后倒入8eqv体积的水并继续搅拌1小时，然后过滤。过滤后的固体用水、乙醇和石油醚分别洗涤两次，再置于烘箱中烘干得到8.10g白色固体L1-1，收率84％。
制备上述路线中化合物L1-2：取6.44g(20mmol)化合物L1-1，225mg(1mmol)Pd(OAc)2，5.52g(40mmol)无水K2CO3，100mL DMAC于250mL的三口瓶中，抽真空，170℃下回流过夜。等到原料反应完全结束后，温度降到室温，将反应液倒进水中，持续搅拌30分钟，再用二氯甲烷萃取三次。萃取液合并浓缩过柱，洗脱剂为DCM:PE＝1:2，得到4.20g白色固体L1-2，收率88％。
制备上述路线中化合物L1-3：取2.41g(10mmol)化合物L1-2溶于100mL二氯甲烷，在26W节能灯下，1.78g(10mmol)NBS分批缓慢加入，室温搅拌12小时。反应结束后析出少量固体，旋干大部分溶剂，在大量固体析出后过滤，所得固体用乙醇洗涤，在真空干燥箱内烘干，得到2.88g白色固体L1-3，收率90％。
制备上述路线中化合物L1-4：取16.00g(50mmol)化合物L1-3，14.00g(55mmol)联硼酸频那醇酯，1.68g(2.5mmol)Pd(dppf)Cl2，10.00g(100mmol)KOAc，300mL二氧六环于500mL的三口瓶中，抽真空，100℃下反应过夜。等到原料全部反应后，温度降到室温，加入水后用EA萃取，水相用二氯甲烷进行三次萃取，萃取液合并浓缩过柱，洗脱剂为DCM：PE＝1:1，得到12.80g白色固体L1-4，收率70％。
制备上述路线中主配体L1：取1.83g(5mmol)化合物4，869mg(5.5mmol)2-溴吡啶，183mg(0.25mmol)Pd(dppf)Cl2，4.89g(15mmol)Cs2CO3，5mL水，50mL二氧六环于200mL两口瓶内，在氮气保护下回流过夜，等到反应结束后，温度降至室温，用短硅胶柱将反应液过滤，加入DCM抽滤，旋干浓缩过柱，洗脱剂为DCM：PE＝2:1，置于烘箱中烘干，得到859mg白色固体L1，收率54％。1H NMR(400MHz,CDCl3)δ8.79–8.74(m,1H),8.63(s,2H),8.14–8.08(m,2H),7.90–7.85(m,1H),7.84–7.75(m,3H),7.56–7.47(m,2H),7.36–7.29(m,2H),7.26–7.20(m,1H).HRMS(MALDI-TOF,m/z):[M]+calcd for C23H14N2,318.1157；found,318.1151。
制备氯桥C1：将IrCl3(1mmol)和L1(2.2mmol)加入反应瓶，在通氮气条件下，加入乙二醇二乙醚/水(20mL/5mL)的混合溶液。在130℃下，回流2小时，反应结束后，温度降到室温，过滤得到氯桥，收率88％。
制备铱配合物Ir01：110℃下，将得到的氯桥中间体(0.5mmol)和乙酰丙酮的钠盐(1.25mmol)在乙二醇二乙醚(20mL)中回流搅拌2小时。完全反应后，减压蒸馏蒸干溶剂，采用DCM进行萃取，旋干后柱层析分离，将得到的产物通过真空提纯，得到黄色固体产物Ir01，收率81％。
Ir01：1H NMR(400MHz,CDCl3)δ8.78–8.72(m,2H),8.68–8.64(m,2H),8.59–8.53(m,2H),8.31(s,2H),8.19–8.12(m,4H),8.09–8.03(m,2H),7.58–7.53(m,4H),7.50–7.44(m，4H)，7.20–7.14(m,4H),5.65(s,1H),0.77(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd forC51H33IrN4O2:924.2209；found:924.2202。
其他配合物按照同样的方法合成Ir02-Ir96：
Ir02：1H NMR(400MHz,CDCl3)δ8.74(s,2H),8.41–8.34(m,2H),8.19–8.15(m,2H),8.14–8.10(m,2H),7.86–7.76(m,4H),7.67–7.62(m,2H),7.47–7.41(m,2H),7.35–7.28(m,2H)，7.16–7.10(m，2H)，6.84–6.77(m，2H)，6.59–6.51(m,2H)，6.45–6.38(m，2H)，5.70(s，1H),0.79(s,18H).HRMS(MALDI-TOF，m/z):[M]+calcd for C57H45IrN4O2:1011.3245；found:1011.3249。
Ir03：1H NMR(400MHz,CDCl3)δ8.61–8.57(m,2H),8.30–8.25(m,2H),8.07–8.04(m,2H),7.87(s,2H),7.75–7.70(m,4H),7.59–7.52(m,2H),7.18–7.11(m,4H),6.95–6.91(m,4H),6.44–6.37(m,4H),6.03(s,1H)，1.77(d，J＝8.2Hz,4H),1.44(s，2H),0.74(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H45IrN4O2:1011.3205；found:1011.3209。
Ir04：1H NMR(400MHz,CDCl3)δ8.53–8.48(m,2H),8.21–8.16(m,2H),8.01–7.95(m,2H),7.80(s,2H),7.65–7.61(m,4H),7.52–7.47(m,2H),7.09–7.01(m,4H),6.87–6.80(m，4H)，6.38–6.32(m,4H),5.84(s,1H),1.27(t,J＝8.4Hz,2H),1.24(m,8H)，0.77(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H49IrN4O2:1039.3518；found:1039.3522。
Ir05：1H NMR(400MHz,CDCl3)δ9.01–8.94(m,2H),8.89–8.83(m,2H),8.75–8.69(m,2H),8.66–8.61(m，2H)，8.58–8.52(m，2H),8.39–8.32(m，2H),8.27–8.21(m,2H),8.04(s,2H),7.81–7.73(m，4H),7.52–7.45(m,4H),5.83(s,1H),0.63(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C49H31IrN6O2:928.2138；found:928.2132。
Ir06：1H NMR(400MHz,CDCl3)δ9.12–9.06(m,2H),8.93–8.87(m,2H),8.86–8.81(m,2H),8.73–8.67(m,2H),8.63–8.57(m,2H),8.44–8.39(m,2H),8.35–8.29(m,2H),8.12(s,2H),7.93–7.88(m,4H),7.67–7.61(m,4H),5.95(s,1H),0.69(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C55H43IrN6O2:1012.3077；found:1012.3083。
Ir07：1H NMR(400MHz,CDCl3)δ9.07–9.01(m,2H),8.90–8.83(m,2H),8.81–8.77(m,2H),8.68–8.62(m,2H),8.58–8.52(m,2H),8.38–8.32(m,2H),8.30–8.24(m,2H),8.06(s,2H),7.85–7.79(m,4H),7.62–7.57(m,4H),5.84(s,1H),1.62–1.57(m,4H),1.33(d,J＝8.4Hz,2H),0.65(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C55H43IrN6O2:1012.3077；found:1012.3074。
Ir08：1H NMR(400MHz,CDCl3)δ9.22–9.17(m,2H),9.10–9.04(m,2H),8.95–8.89(m,2H),8.82–8.76(m,2H),8.74–8.68(m,2H),8.54–8.49(m,2H),8.43–8.37(m,2H),8.24(s,2H),8.02–7.96(m,4H),7.83–7.76(m,4H),5.92(s,1H),1.71–1.65(m,2H),1.47–1.41(m,8H),0.72(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H47IrN6O2:1040.3390；found:1040.3392。
Ir09：1H NMR(400MHz,CDCl3)δ9.22–9.17(m,2H),9.04–8.97(m,2H),8.93–8.86(m,2H),8.79–8.70(m,4H),8.62–8.49(m,4H),8.45(s,2H),8.28–8.22(m,2H),7.41–7.25(m,4H),5.88(s,1H),0.76(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C47H29IrN8O2:928.2019；found:928.2011。
Ir10：1H NMR(400MHz,CDCl3)δ9.28–9.23(m,2H),9.13–9.08(m,2H),8.99–8.93(m,2H),8.85–8.71(m,4H),8.69–8.50(m,4H),8.54(s,2H),8.34–8.28(m,2H),7.49–7.32(m,4H),5.93(s,1H),0.79(s,18H).HRMS(MALDI-TOF，m/z):[M]+calcd for C53H41IrN8O2:1012.2958；found:1012.2963。
Ir11：1H NMR(400MHz，CDCl3)δ9.33–9.29(m,2H),9.15–9.09(m,2H),9.04–8.98(m,2H),8.91–8.77(m，4H),8.75–8.58(m,4H),8.59(s,2H),8.38–8.34(m,2H)，7.53–7.39(m,4H),5.98(s,1H),1.45–1.40(m,4H),1.18(d,J＝8.4Hz,2H),0.71(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C53H41IrN8O2:1012.2958；found:1012.2961。
Ir12：1H NMR(400MHz,CDCl3)δ9.25–9.20(m,2H),9.07–9.01(m,2H),8.96–8.89(m，2H),8.84–8.71(m，4H),8.67–8.50(m,4H),8.51(s,2H),8.30–8.25(m,2H),7.44–7.32(m,4H),5.89(s,1H),1.43–1.36(m,2H),1.17–1.11(m,8H)，0.73(s，12H).HRMS(MALDI-TOF，m/z):[M]+calcd for C55H45IrN8O2:1040.3271；found:1040.3269。
Ir13：1H NMR(400MHz，CDCl3)δ8.98–8.94(m，2H),8.86–8.80(m，2H),8.54(s，2H),8.39–8.32(m，4H)，7.95–7.89(m，2H),7.81–7.74(m,4H),7.68–7.64(m，4H),7.50–7.44(m，4H),5.90(s,1H),0.81(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C53H31F6IrN4O2:1060.1957；found:1060.1967。
Ir14：1H NMR(400MHz,CDCl3)δ8.80(s,2H),8.59–8.52(m,2H),8.28–8.23(m,2H),8.23–8.17(m,2H),7.82–7.76(m,2H),7.72–7.64(m,2H),7.51–7.43(m,2H),7.39–7.30(m,2H),7.23–7.14(m,2H),7.00(dd,J＝6.1,1.8Hz,2H),6.64–6.54(m,4H),6.36–6.30(m,2H),0.80(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H43F6IrN4O2:1147.2992；found:1147.2992。
Ir15：1H NMR(400MHz,CDCl3)δ8.77(s,2H),8.55–8.48(m,2H),8.22–8.17(m,2H),8.14–8.09(m,2H),7.72–7.65(m,2H),7.60–7.51(m,2H),7.43–7.39(m,2H),7.27–7.19(m,2H),7.13–7.04(m，2H),6.95–6.88(m,2H),6.53–6.42(m,4H),6.19–6.12(m,2H),6.23(s,1H),1.85(d,J＝8.2Hz,2H),1.58(s,2H),0.91(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcdfor C59H43F6IrN4O2:1147.2953；found:1147.2959。
Ir16：1H NMR(400MHz,CDCl3)δ8.62(s,2H),8.43–8.37(m,2H),8.14–8.07(m,2H),8.02–7.89(m,2H),7.57–7.51(m,2H),7.45–7.39(m,2H),7.28–7.22(m,2H),7.09–7.01(m,2H),6.92–6.84(m,2H),6.75–6.68(m,2H),6.18–6.12(m,4H),6.07–5.99(m,2H),5.73(s,1H),1.79(d,J＝8.4Hz,2H),1.52(s,8H),0.88(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcdfor C61H47F6IrN4O2:1175.3266；found:1175.3261。
Ir17：1H NMR(400MHz,CDCl3)δ9.55–9.50(m,2H),9.43–9.36(m,2H),9.29–9.24(m,2H),9.09–9.03(m,2H),8.87–8.81(m,2H),8.32(s,2H),8.13–8.07(m,2H),7.98–7.87(m,4H),7.43–7.32(m,4H),5.82(s,1H),0.75(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd forC51H29F6IrN6O2:1062.1862；found:1062.1860。
Ir18：1H NMR(400MHz,CDCl3)δ9.47–9.42(m,2H),9.38–9.32(m,2H),9.21–9.16(m,2H),8.98–8.91(m,2H),8.79–8.71(m,2H),8.24(s,2H),8.02–7.94(m,2H),7.86–7.72(m,4H),7.35–7.23(m,4H),5.75(s,1H),0.71(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd forC57H41F6IrN6O2:1149.2858；found:1149.2852。
Ir19：1H NMR(400MHz,CDCl3)δ9.50–9.45(m,2H),9.42–9.38(m,2H),9.25–9.19(m,2H),9.02–8.96(m,2H),8.83–8.78(m,2H),8.27(s,2H),8.05–7.99(m,2H),7.89–7.75(m,4H),7.41–7.29(m,4H),5.79(s,1H),1.55–1.49(m,4H),1.27(d,J＝8.4Hz,2H),0.73(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H41F6IrN6O2:1149.2858；found:1149.2855。
Ir20：1H NMR(400MHz,CDCl3)δ9.41–9.36(m,2H),9.33–9.27(m,2H),9.14–9.08(m,2H),8.91–8.85(m,2H),8.72–8.67(m,2H),8.13(s,2H),7.92–7.87(m,2H),7.72–7.59(m,4H),7.28–7.11(m,4H),5.63(s,1H),1.51–1.46(m,2H),1.21–1.15(m,8H),0.67(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H45F6IrN6O2:1177.3171；found:1177.3175。
Ir21：1H NMR(400MHz,CDCl3)δ9.29–9.21(m,2H),9.12–9.07(m,2H),9.03–8.81(m,4H),8.64–8.51(m,4H),8.32(s,2H),7.98–7.93(m,2H),7.48–7.32(m,4H),5.60(s,1H),0.68(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C49H27F6IrN8O2:1064.1767；found:1064.1761。
Ir22：1H NMR(400MHz,CDCl3)δ9.20–9.13(m,2H),9.01–8.99(m,2H),8.94–8.73(m,4H),8.56–8.35(m,4H),8.21(s,2H),7.87–7.76(m,2H),7.39–7.24(m,4H),5.52(s,1H),0.64(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C55H39F6IrN8O2:1148.2706；found:1148.2708。
Ir23：1H NMR(400MHz,CDCl3)δ9.12–9.05(m,2H),8.93–8.86(m,2H),8.85–8.66(m,4H),8.48–8.28(m,4H),8.15(s,2H),7.80–7.71(m,2H),7.31–7.17(m,4H),5.45(s,1H),1.53–1.38(m,4H),1.26(d,J＝8.4Hz,2H),0.75(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcdfor C55H39F6IrN8O2:1148.2706；found:1148.2706。
Ir24：1H NMR(400MHz,CDCl3)δ9.08–9.01(m,2H),8.88–8.82(m,2H),8.80–8.61(m,4H),8.44–8.23(m,4H),8.11(s,2H),7.77–7.68(m,2H),7.27–7.12(m,4H),5.40(s,1H),1.48–1.41(m,2H),1.19–1.10(m,8H),0.71(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd forC57H43F6IrN8O2:1179.3076；found:1179.3072。
Ir25：1H NMR(400MHz,CDCl3)δ10.35–10.28(m，2H),10.24–10.17(m,2H),8.85–8.71(m,4H),8.23(s,2H),8.17–8.11(m,2H),7.84–7.70(m,4H),7.65–7.49(m,4H),7.35–7.18(m,4H),5.54(s,1H),0.68(s,6H).HRMS(MALDI-TOF，m/z):[M]+calcd forC49H31IrN6O2:926.2114；found:926.2115。
Ir26：1H NMR(400MHz，CDCl3)δ10.12–10.06(m，2H),10.02–9.97(m，2H),8.63–8.50(m,4H),8.01(s,2H),7.95–7.87(m,2H),7.63–7.48(m,4H),7.44–7.27(m,4H),7.17–7.00(m,4H),5.46(s,1H),0.65(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C55H43IrN6O2:1010.3053；found:1010.3053。
Ir27：1H NMR(400MHz,CDCl3)δ10.19–10.13(m,2H),10.10–10.02(m,2H),8.71–8.57(m,4H),8.09(s,2H),8.01–7.95(m,2H),7.69–7.54(m,4H),7.51–7.35(m,4H),7.23–7.09(m,4H),5.49(s,1H),1.41–1.27(m,4H),1.13(d,J＝8.4Hz，2H),0.67(s，12H).HRMS(MALDI-TOF，m/z):[M]+calcd for C55H43IrN6O2:1010.3053；found:1010.3057。
Ir28：1H NMR(400MHz,CDCl3)δ10.24–10.18(m,2H),10.15–10.07(m,2H),8.77–8.63(m,4H),8.15(s,2H),8.06–7.98(m,2H),7.77–7.59(m,4H),7.56–7.37(m,4H),7.29–7.14(m,4H),5.53(s,1H),1.41–1.36(m,2H),1.12–1.04(m,8H),0.68(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H47IrN6O2:1041.3423；found:1041.3422。
Ir29：1H NMR(400MHz,CDCl3)δ10.51–10.47(m,2H),10.45–10.38(m,2H),9.34–9.28(m,2H),9.17–9.12(m,2H),8.89–8.84(m,2H),8.64(s,2H),8.61–8.54(m,2H),8.30–8.11(m,4H),7.97–7.74(m,4H),5.54(s,1H),0.82(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C47H29IrN8O2:928.2019；found:928.2015。
Ir30：1H NMR(400MHz,CDCl3)δ10.42–10.37(m,2H),10.34–10.28(m,2H),9.25–9.18(m,2H),9.09–9.01(m,2H),8.80–8.73(m,2H),8.56(s,2H),8.52–8.45(m,2H),8.23–8.02(m,4H),7.88–7.61(m,4H),5.49(s,1H),0.78(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C53H41IrN8O2:1012.2958；found:1012.2960。
Ir31：1H NMR(400MHz,CDCl3)δ10.46–10.40(m,2H),10.39–10.33(m,2H),9.28–9.22(m,2H),9.14–9.07(m,2H),8.86–8.79(m,2H),8.61(s,2H),8.58–8.51(m,2H),8.28–8.09(m,4H),7.92–7.68(m,4H),5.51(s,1H),1.54–1.43(m,4H),1.31(d,J＝8.4Hz,2H),0.85(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C53H41IrN8O2:1012.2958；found:1012.2960。
Ir32：1H NMR(400MHz,CDCl3)δ10.33–10.27(m,2H),10.25–10.19(m,2H),9.14–9.08(m,2H),9.01–8.95(m,2H),8.71–8.66(m,2H),8.47(s,2H),8.45–8.39(m,2H),8.13–7.95(m,4H),7.80–7.54(m,4H),5.44(s,1H)，1.38–1.21(m，2H)，1.10–1.01(m,8H),0.64(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C55H45IrN8O2:1040.3271；found:1040.3269。
Ir33：1H NMR(400MHz,CDCl3)δ10.62–10.56(m,2H),10.53–10.46(m,2H),9.41–9.32(m,4H),9.29–9.15(m,4H),9.11(s,2H),8.69–8.61(m,2H),8.07–7.92(m,4H),5.47(s,1H),0.75(s，6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C45H27IrN10O2:930.1924；found:930.1922。
Ir34：1H NMR(400MHz，CDCl3)δ10.44–10.38(m,2H),10.34–10.27(m,2H),9.24–9.06(m,4H),9.06–8.97(m,4H),8.93(s,2H),8.51–8.45(m,2H)，7.88–7.69(m,4H),5.36(s,1H),0.66(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C51H39IrN10O2:1014.2863；found:1014.2866。
Ir35：1H NMR(400MHz,CDCl3)δ10.56–10.49(m,2H),10.45–10.39(m,2H)，9.37–9.27(m,4H),9.25–9.11(m,4H),9.05(s，2H),8.64–8.59(m,2H),7.99–7.81(m,4H),5.41(s,1H),1.39–1.25(m,4H),1.17(d,J＝8.4Hz,2H),0.74(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C51H39IrN10O2:1014.2863；found:1014.2862。
Ir36：1H NMR(400MHz,CDCl3)δ10.39–10.32(m，2H),10.29–10.22(m,2H),9.19–9.09(m,4H),9.08–8.94(m,4H),8.89(s，2H),8.46–8.39(m,2H),7.82–7.63(m,4H),5.26(s,1H),1.29–1.19(m,2H),1.13–1.05(m,8H),0.62(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcdfor C53H43IrN10O2:1042.3176；found:1042.3175。
Ir37：1H NMR(400MHz，CDCl3)δ9.47–9.41(m,2H),9.30–9.23(m,2H)，9.22–9.11(m,4H),9.09–9.02(m,2H),8.98–8.90(m,4H),8.90–8.81(m，2H)，8.67(s，2H),8.38–8.12(m,8H),8.01–7.84(m,4H),5.72(s,1H),0.86(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd forC59H37IrN4O2:1027.2579；found:1027.2580。
Ir38：1H NMR(400MHz,CDCl3)δ9.24–9.18(m,2H),9.06–9.01(m,2H),9.00–8.89(m,4H),8.87–8.81(m，2H)，8.75–8.67(m，4H),8.65–8.59(m，2H),8.41(s,2H),8.15–7.88(m,8H),7.83–7.61(m,4H),5.57(s,1H),0.75(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd forC65H49IrN4O2:1111.3518；found:1111.3515。
Ir39：1H NMR(400MHz,CDCl3)δ9.53–9.47(m,2H),9.37–9.32(m,2H),9.28–9.22(m,4H),9.15–9.09(m,2H),9.02–8.94(m,4H),8.93–8.85(m,2H),8.68(s,2H),8.42–8.26(m,8H),8.12–7.87(m,4H),5.84(s,1H),1.46–1.34(m，4H),1.31(d,J＝8.4Hz,2H),0.91(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C65H49IrN4O2:1111.3518；found:1111.3519。
Ir40：1H NMR(400MHz,CDCl3)δ9.40–9.34(m,2H),9.23–9.17(m,2H),9.14–9.22(m,4H),9.01–8.95(m,2H),8.87–8.80(m,4H),8.78–8.71(m,2H),8.54(s,2H),8.29–8.11(m,8H),8.00–7.79(m,4H),5.70(s,1H),1.38–1.31(m,2H),1.25–1.13(m,8H),0.79(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C67H53IrN4O2:1139.3831；found:1139.3830。
Ir41：1H NMR(400MHz,CDCl3)δ9.82–9.76(m,2H),9.71–9.61(m,4H),9.59–9.50(m,6H),9.49–9.44(m,2H),9.38–9.31(m,2H),9.30–9.23(m，2H)，9.04(s，2H),8.78–8.55(m,4H),8.37–8.24(m,4H),5.91(s,1H),0.96(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd forC57H35IrN6O2:1029.2484；found:1029.2481。
Ir42：1H NMR(400MHz,CDCl3)δ9.47–9.41(m,2H),9.37–9.25(m,4H),9.23–9.17(m,6H),9.14–9.08(m,2H),9.02–8.97(m,2H),8.95–8.89(m,2H),8.70(s,2H),8.42–8.31(m,4H),8.01–7.86(m,4H),5.75(s,1H),0.77(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd forC63H47IrN6O2:1113.3423；found:1113.3425。
Ir43：1H NMR(400MHz,CDCl3)δ9.89–9.82(m,2H),9.80–9.67(m,4H),9.67–9.58(m,6H),9.57–9.53(m,2H),9.44–9.38(m,2H),9.36–9.31(m,2H),9.13(s,2H),8.87–8.72(m,4H),8.45–8.23(m,4H),5.96(s,1H),1.65–1.54(m,4H),1.49(d,J＝8.4Hz,2H),0.92(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C63H47IrN6O2:1113.3423；found:1113.3423。
Ir44：1H NMR(400MHz,CDCl3)δ9.64–9.58(m,2H),9.55–9.43(m,4H),9.42–9.32(m,6H),9.30–9.23(m,2H),9.17–9.11(m,2H),9.10–9.04(m,2H),8.88(s,2H),8.64–8.51(m,4H),8.23–8.08(m,4H),5.83(s,1H),1.55–1.49(m,2H),1.36–1.24(m,8H),0.89(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C65H51IrN6O2:1141.3736；found:1141.3737。
Ir45：1H NMR(400MHz,CDCl3)δ9.68–9.62(m,2H),9.50–9.40(m,6H),9.39–9.32(m,8H),9.31(s,2H),9.29–9.21(m,2H),9.10–9.03(m,2H),8.17–8.11(m,4H),5.82(s,1H),0.93(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C55H33IrN8O2:1028.2332；found:1028.2334。
Ir46：1H NMR(400MHz,CDCl3)δ9.34–9.28(m,2H),9.17–9.08(m,6H),9.06–8.96(m,8H),8.95(s,2H),8.93–8.87(m,2H),8.76–8.70(m,2H),7.82–7.71(m,4H),5.57(s,1H),0.79(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C61H45IrN8O2:1115.3328；found:1115.3325。
Ir47：1H NMR(400MHz,CDCl3)δ9.75–9.69(m,2H),9.59–9.49(m,6H),9.48–9.40(m,8H),9.36(s,2H),9.35–9.28(m,2H),9.15–9.08(m,2H),8.23–8.12(m,4H),5.87(s,1H),1.52–1.41(m,4H),1.35(d,J＝8.4Hz,2H),0.95(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcdfor C61H45IrN8O2:1115.3328；found:1115.3325。
Ir48：1H NMR(400MHz,CDCl3)δ9.56–9.51(m,2H),9.41–9.29(m,6H),9.27–9.19(m,8H),9.15(s,2H),9.13–9.07(m,2H),8.92–8.85(m,2H),8.03–7.91(m,4H),5.75(s,1H),1.43–1.36(m,2H),1.29–1.18(m,8H),0.85(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd forC63H49IrN8O2:1143.3641；found:1143.3644。
Ir49：1H NMR(400MHz,CDCl3)δ9.20(s,2H),8.19–8.13(m,4H),7.84–7.80(m,6H),8.21–8.14(m,4H),7.58–7.50(m,8H),7.20–7.18(m,4H),5.91(s,1H),0.96(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H35IrN6O2,1029.2484；found,1029.2485。
Ir50：1H NMR(400MHz,CDCl3)δ9.20(s,2H),8.19–8.14(m,4H),7.84–7.83(m,6H),8.21–8.11(m,4H),7.58–7.50(m,8H),7.20–7.17(m,4H),5.75(s,1H),0.77(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C63H47IrN6O2,1113.3423；found,1113.3421。
Ir51：1H NMR(400MHz,CDCl3)δ9.20(s,2H),8.20–8.13(m,4H),7.85–7.83(m,6H),8.22–8.14(m,4H),7.58–7.50(m,8H),7.20–7.17(m,4H),5.96(s,1H),1.65–1.54(m,4H),1.49(d,J＝8.4Hz,2H),0.92(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C63H47IrN6O2,1113.3423；found,1113.3425。
Ir52：1H NMR(400MHz,CDCl3)δ9.20(s,2H),8.20–8.13(m,4H),7.85–7.83(m,6H),8.22–8.14(m,4H),7.58–7.50(m,8H),7.20–7.17(m,4H),5.83(s,1H),1.55–1.49(m,2H),1.36–1.24(m,8H),0.89(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C65H51IrN6O2,1141.3736；found,1141.3733。
Ir53：1H NMR(400MHz,CDCl3)δ9.20(s,2H),8.51–8.45(m,2H),8.39–8.31(m,2H),8.19–8.13(m,4H),7.84–7.83(m,6H),7.58–7.50(m,6H),7.20–7.17(m,4H),5.91(s，1H),0.96(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C55H33IrN8O2,1031.2590；found,1031.2565。
Ir54：1H NMR(400MHz,CDCl3)δ9.20(s，2H),8.51–8.45(m,2H),8.39–8.31(m,2H)，8.19–8.13(m,4H),7.84–7.83(m,6H),7.58–7.50(m,6H),7.20–7.17(m,4H),5.75(s,1H),0.77(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C61H45IrN8O2,1115.3529；found,1115.3260。
Ir55：1H NMR(400MHz,CDCl3)δ9.20(s,2H),8.51–8.45(m,2H),8.39–8.31(m,2H),8.19–8.13(m,4H),7.84–7.83(m,6H),7.58–7.50(m,6H),7.20–7.17(m,4H),5.96(s,1H),1.65–1.54(m,4H),1.49(d,J＝8.4Hz,2H),0.92(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcdfor C61H45IrN8O2,1115.3529；found,1115.3263。
Ir56：1H NMR(400MHz,CDCl3)δ9.20(s,2H),8.51–8.45(m,2H),8.39–8.31(m,2H),8.19–8.13(m,4H),7.84–7.83(m,6H),7.58–7.50(m,6H),7.20–7.17(m,4H),5.83(s,1H),1.55–1.49(m,2H),1.36–1.24(m,8H),0.89(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd forC63H49IrN8O2,1143.3842；found,1143.3800。
Ir57：1H NMR(400MHz，CDCl3)δ9.20(s,2H),8.51–8.45(m,4H),8.39–8.31(m,6H),8.13–8.11(m,2H),7.84–7.83(m，4H),7.58–7.54(m,2H),7.21–7.17(m,4H)，5.91(s,1H),0.96(s，6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C53H31IrN10O2,1033.2261；found,1033.2261。
Ir58：1H NMR(400MHz,CDCl3)δ9.20(s,2H),8.51–8.45(m,4H),8.39–8.31(m,6H),8.13–8.11(m,2H),7.84–7.83(m,4H),7.58–7.54(m,2H),7.21–7.17(m,4H),5.75(s,1H),0.77(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H43IrN10O2,1117.3434；found,1117.3020。
Ir59：1H NMR(400MHz,CDCl3)δ9.20(s,2H),8.51–8.45(m,4H),8.39–8.31(m,6H),8.13–8.11(m,2H),7.84–7.83(m,4H),7.58–7.54(m,2H),7.21–7.17(m,4H),5.96(s,1H),1.65–1.54(m,4H),1.49(d,J＝8.4Hz,2H),0.92(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcdfor C59H43IrN10O2,1117.3434；found,1117.3468。
Ir60：1H NMR(400MHz,CDCl3)δ9.20(s,2H),8.51–8.45(m,4H),8.39–8.31(m,6H),8.13–8.11(m,2H),7.84–7.83(m,4H),7.58–7.54(m,2H),7.21–7.17(m,4H),5.83(s,1H),1.55–1.49(m,2H),1.36–1.24(m,8H),0.89(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd forC61H47IrN10O2,1145.3747；found,1145.3560。
Ir61：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.46(m,2H),8.39–8.34(m,2H),8.19–8.14(m,4H),7.84–7.80(m,2H),7.58–7.50(m,8H),7.36–7.34(m,2H),7.20–7.15(m,4H),5.91(s,1H),0.96(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C55H33IrN8O2,1031.2590；found,1031.2567。
Ir62：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.46(m,2H),8.39–8.34(m,2H),8.19–8.14(m,4H),7.84–7.80(m,2H),7.58–7.50(m,8H),7.36–7.34(m,2H),7.20–7.15(m,4H),5.75(s,1H),0.77(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C61H45IrN8O2,1115.3529；found,1115.3263。
Ir63：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.46(m,2H),8.39–8.34(m,2H),8.19–8.14(m,4H),7.84–7.80(m,2H),7.58–7.50(m,8H),7.36–7.34(m,2H),7.20–7.15(m,4H),5.96(s,1H),1.65–1.54(m,4H),1.49(d,J＝8.4Hz,2H),0.92(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C61H45IrN8O2,1115.3529；found,1115.3260。
Ir64：1H NMR(400MHz，CDCl3)δ9.23(s,2H),8.51–8.46(m,2H),8.39–8.34(m,2H),8.19–8.14(m，4H),7.84–7.80(m,2H),7.58–7.50(m,8H),7.36–7.34(m,2H),7.20–7.15(m,4H),5.83(s,1H),1.55–1.49(m,2H),1.36–1.24(m,8H),0.89(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C63H49IrN8O2,1143.3842；found,1143.3876。
Ir65：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.46(m,4H),8.39–8.36(m,4H),8.19–8.16(m,2H),7.84(s，2H),7.58–7.50(m,4H),7.36–7.33(m,2H),7.20–7.17(m,4H)5.65(s,1H),0.77(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C53H31IrN10O2,1033.2495；found,1033.1400。
Ir66：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.46(m,4H),8.39–8.36(m,4H),8.19–8.16(m,2H),7.84(s,2H),7.58–7.50(m,4H),7.36–7.33(m,2H),7.20–7.17(m,4H),5.70(s,1H),0.79(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H43IrN10O2,1117.3434；found,1117.3468。
Ir67：1H NMR(400MHz,CDCl3)δ9.23(s，2H),8.51–8.46(m,4H),8.39–8.36(m,4H)，8.19–8.16(m,2H),7.84(s,2H),7.58–7.50(m,4H),7.36–7.33(m,2H),7.20–7.17(m,4H),6.03(s,1H),1.77(d,J＝8.2Hz,4H),1.44(s,2H),0.74(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H43IrN10O2,1117.3434；found,1117.3020。
Ir68：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.46(m,4H),8.39–8.36(m,4H),8.19–8.16(m,2H),7.84(s,2H),7.58–7.50(m,4H),7.36–7.33(m,2H),7.20–7.17(m,4H),5.84(s,1H),1.27(t,J＝8.4Hz,2H),1.24(m,8H),0.77(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C61H47IrN10O2,1117.3434；found,1117.3020。
Ir69：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.46(m,6H),8.39–8.36(m,6H),8.31(s,2H),7.36–7.34(m,2H),7.17–7.13(m,4H),5.65(s,1H),0.77(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C51H29IrN12O2,1035.2400；found,1035.1166。
Ir70：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.46(m,6H),8.39–8.36(m,6H),8.31(s,2H),7.36–7.34(m,2H),7.17–7.13(m,4H),5.70(s,1H),0.79(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H41IrN12O2,1119.3339；found,1119.3373。
Ir71：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.46(m,6H),8.39–8.36(m,6H),8.31(s,2H),7.36–7.34(m,2H),7.17–7.13(m,4H),6.03(s,1H),1.77(d,J＝8.2Hz,4H),1.44(s,2H),0.74(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H41IrN12O2,1119.3339；found,1119.2780。
Ir72：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.46(m,6H),8.39–8.36(m,6H),8.31(s,2H),7.36–7.34(m,2H),7.17–7.13(m,4H),5.84(s,1H),1.27(t,J＝8.4Hz,2H),1.24(m,8H),0.77(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H45IrN12O2,1147.3652；found,1147.3686。
Ir73：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.19–8.13(m,6H),7.84(s,2H),7.58–7.50(m,8H),7.42–7.38(m,2H),7.20–7.16(m,4H)，5.65(s,1H),0.77(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C53H31IrN6O4,1009.2271；found,1009.2247。
Ir74：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.19–8.13(m,6H),7.84(s,2H),7.58–7.50(m,8H),7.42–7.38(m,2H),7.20–7.16(m,4H),5.70(s,1H),0.79(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H43IrN6O4,1092.3210；found,1092.2720。
Ir75：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.19–8.13(m,6H),7.84(s,2H),7.58–7.50(m,8H),7.42–7.38(m,2H),7.20–7.16(m,4H),6.03(s,1H),1.77(d,J＝8.2Hz,4H),1.44(s,2H),0.74(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H43IrN6O4,1092.3210；found,1092.3243。
Ir76：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.19–8.13(m,6H),7.84(s,2H),7.58–7.50(m,8H),7.42–7.38(m,2H),7.20–7.16(m,4H),5.84(s,1H),1.27(t,J＝8.4Hz,2H),1.24(m,8H),0.77(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C61H47IrN6O4,1121.3527；found,1121.3260。
Ir77：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.45(m,2H),8.39–8.36(m,2H),8.19–8.13(m,4H),7.84(s,2H),7.58–7.50(m,4H),7.42–7.38(m,2H),7.20–7.17(m,4H),5.65(s,1H),0.77(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C51H29IrN8O4,1011.2176；found,1011.0860。
Ir78：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.45(m,2H),8.39–8.36(m,2H),8.19–8.13(m,4H),7.84(s,2H),7.58–7.50(m,4H)，7.42–7.38(m,2H),7.20–7.17(m,4H),5.70(s,1H),0.79(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H41IrN8O4,1095.3115；found,1095.3148。
Ir79：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.45(m,2H),8.39–8.36(m,2H),8.19–8.13(m,4H),7.84(s,2H),7.58–7.50(m,4H),7.42–7.38(m，2H),7.20–7.17(m,4H),6.03(s,1H),1.77(d,J＝8.2Hz,4H),1.44(s,2H),0.74(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H41IrN8O4,1095.3115；found,1095.2480。
Ir80：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.45(m,2H),8.39–8.36(m,2H),8.19–8.13(m,4H),7.84(s,2H),7.58–7.50(m,4H),7.42–7.38(m,2H),7.20–7.17(m,4H),5.84(s,1H)，1.27(t,J＝8.4Hz,2H),1.24(m,8H),0.77(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H45IrN8O4,1123.3428；found,1123.3020。
Ir81：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.45(m,4H),8.39–8.36(m,4H),8.31(s,2H),8.16–8.13(m,2H),7.42–7.38(m,2H)，7.20–7.17(m,4H),5.65(s,1H)，0.77(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C49H27IrN10O4,1013.2081；found,1013.0620。
Ir82：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.45(m,4H),8.39–8.36(m,4H),8.31(s,2H),8.16–8.13(m,2H),7.42–7.38(m,2H),7.20–7.17(m,4H),5.70(s,1H),0.79(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C55H39IrN10O4,1097.3020；found,1097.2240。
Ir83：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.45(m,4H),8.39–8.36(m,4H),8.31(s,2H),8.16–8.13(m,2H),7.42–7.38(m,2H),7.20–7.17(m,4H),6.03(s,1H),1.77(d,J＝8.2Hz,4H),1.44(s,2H),0.74(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd forC55H39IrN10O4,1097.3020；found,1097.2996。
Ir84：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.45(m,4H),8.39–8.36(m,4H),8.31(s,2H),8.16–8.13(m,2H),7.42–7.38(m,2H),7.20–7.17(m,4H),5.84(s,1H),1.27(t,J＝8.4Hz,2H),1.24(m,8H),0.77(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd forC57H43IrN10O4,1125.3333；found,1125.2780。
Ir85：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.19–8.13(m,4H),7.84(s,2H),7.58–7.50(m,8H),7.33–7.31(m,2H),7.20–7.12(m,6H),5.65(s,1H),0.77(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C53H31IrN6O2S2,1041.1814；found,1041.2320。
Ir86：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.19–8.13(m,4H),7.84(s,2H),7.58–7.50(m,8H),7.33–7.31(m,2H),7.20–7.12(m,6H),5.70(s,1H),0.79(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H43IrN6O2S2,1125.2753；found,1125.3940。
Ir87：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.19–8.13(m,4H),7.84(s,2H),7.58–7.50(m,8H),7.33–7.31(m,2H),7.20–7.12(m,6H),6.03(s,1H),1.77(d,J＝8.2Hz,4H),1.44(s,2H),0.74(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H43IrN6O2S2,1125.2753；found,1125.2786。
Ir88：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.19–8.13(m,4H),7.84(s,2H),7.58–7.50(m,8H),7.33–7.31(m,2H),7.20–7.12(m,6H),5.84(s,1H),1.27(t,J＝8.4Hz,2H),1.24(m,8H),0.77(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C61H47IrN6O2S2,1153.4066；found,1153.4480。
Ir89：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.47(m,2H),8.39–8.36(m,2H),8.19–8.15(m,2H),7.84(s，2H),7.58–7.50(m,4H),7.33–7.31(m,2H),7.20–7.12(m，6H),5.65(s,1H),0.77(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C51H29IrN8O2S2,1043.1719；found,1043.2080。
Ir90：1H NMR(400MHz,CDCl3)δ9.23(s，2H),8.51–8.47(m,2H),8.39–8.36(m,2H)，8.19–8.15(m,2H),7.84(s,2H),7.58–7.50(m,4H),7.33–7.31(m,2H),7.20–7.12(m,6H),5.70(s,1H),0.79(s,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H41IrN8O2S2,1127.2658；found,1127.3700。
Ir91：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.47(m,2H),8.39–8.36(m,2H),8.19–8.15(m,2H),7.84(s,2H),7.58–7.50(m,4H),7.33–7.31(m,2H),7.20–7.12(m,6H),6.03(s,1H),1.77(d,J＝8.2Hz,4H),1.44(s,2H),0.74(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H41IrN8O2S2,1127.2658；found,1127.2691。
Ir92：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.47(m,2H),8.39–8.36(m,2H),8.19–8.15(m,2H),7.84(s,2H),7.58–7.50(m,4H),7.33–7.31(m,2H),7.20–7.12(m,6H),5.84(s,1H),1.27(t,J＝8.4Hz,2H),1.24(m,8H),0.77(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C59H45IrN8O2S2,1155.2971；found,1155.4240。
Ir93：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.47(m,4H),8.39–8.36(m,4H),8.31(s,2H),7.33–7.31(m,2H),7.17–7.12(m,6H),5.65(s,1H),0.77(s,6H).HRMS(MALDI-TOF,m/z):[M]+calcd for C49H27IrN10O2S2，1045.1624；found,1045.1840。Ir94：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.47(m,4H),8.39–8.36(m，4H),8.31(s,2H),7.33–7.31(m,2H),7.17–7.12(m,6H),5.70(s,1H),0.89–0.84(m,18H).HRMS(MALDI-TOF,m/z):[M]+calcd for C55H39IrN10O2S2,1129.2563；found,1129.3460。
Ir95：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.47(m,4H),8.39–8.36(m,4H),8.31(s,2H),7.33–7.31(m,2H),7.17–7.12(m,6H),6.03(s,1H),1.77(d,J＝8.2Hz,4H),1.44(s,2H),0.74(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C55H39IrN10O2S2,1129.2563；found,1129.2540。
Ir96：1H NMR(400MHz,CDCl3)δ9.23(s,2H),8.51–8.47(m,4H),8.39–8.36(m,4H),8.31(s,2H),7.33–7.31(m,2H),7.17–7.12(m,6H),5.84(s,1H),1.27(t,J＝8.4Hz,2H),1.24(m,8H),0.77(s,12H).HRMS(MALDI-TOF,m/z):[M]+calcd for C57H43IrN10O2S2,1157.2876；found,1157.4000。
实施例2铱配合物Ir01有机电致发光器件的制备
OLEDs器件的结构包括：基片、阳极、空穴注入材料、空穴传输层、有机发光层、电子传输层、电子注入材料和阴极。所述基片为玻璃，阳极为铟锡氧，空穴注入层为2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(HAT-CN，5nm)，蒸镀速率为0.05nm/s；空穴层采用4,4'-环己基二[N,N-二(4-甲基苯基)苯胺(TAPC，50nm)，蒸镀速率为0.05nm/s；电子传输层采用1,3,5-三[(3-吡啶基)-3-苯基]苯(TmPyPb，50nm)，蒸镀速率为0.05nm/s；电子注入材料为LiF(1nm)，蒸镀速率为0.01nm/s；阴极为金属Al(100nm)，蒸镀速率为0.2nm/s；所述有机发光层采用掺杂结构，厚度为10nm，包括主体材料和发光材料，所述主体材料是用2，6-双((9H-咔唑-9-基)-3，1-亚苯基)吡啶(2,6DCzPPy)，发光材料为铱配合物Ir01，铱配合物质量分数5wt％。器件性能如表1所示。几种功能材料结构如下所示。
实施例3铱配合物Ir05有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir05，器件性能如表1所示。
实施例4铱配合物Ir09有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir09，器件性能如表1所示。
实施例5铱配合物Ir13有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir13，器件性能如表1所示。
实施例6铱配合物Ir17有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir17，器件性能如表1所示。
实施例7铱配合物Ir21有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir21，器件性能如表1所示。
实施例8铱配合物Ir25有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir25，器件性能如表1所示。
实施例9铱配合物Ir29有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir29，器件性能如表1所示。
实施例10铱配合物Ir33有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir33，器件性能如表1所示。
实施例11铱配合物Ir37有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir37，器件性能如表1所示。
实施例12铱配合物Ir41有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir41，器件性能如表1所示。
实施例13铱配合物Ir45有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir45，器件性能如表1所示。
实施例14铱配合物Ir49有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir49，器件性能如表1所示。
实施例15铱配合物Ir53有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir53，器件性能如表1所示。
实施例16铱配合物Ir57有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir57，器件性能如表1所示。
实施例17铱配合物Ir61有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir61，器件性能如表1所示。
实施例18铱配合物Ir65有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir65，器件性能如表1所示。
实施例19铱配合物Ir69有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir69，器件性能如表1所示。
实施例20铱配合物Ir73有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir73，器件性能如表1所示。
实施例21铱配合物Ir77有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir77，器件性能如表1所示。
实施例22铱配合物Ir81有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir81，器件性能如表1所示。
实施例23铱配合物Ir85有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir85，器件性能如表1所示。
实施例24铱配合物Ir89有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir89，器件性能如表1所示。
实施例25铱配合物Ir93有机电致发光器件的制备
与实施例2的不同之处在于使用的发光材料为铱配合物Ir93，器件性能如表1所示。
表1.本发明部分铱配合物制备的器件性能参数。
| 器件实例 | 发光材料 | 启动电压(V) | 电流效率(cd/A) | 功率效率(lm/W) | 外量子效率(％) |
| 实施例2 | Ir01 | 3.6 | 69.2 | 36.8 | 21.2 |
| 实施例3 | Ir05 | 3.5 | 70.4 | 38.5 | 22.1 |
| 实施例4 | Ir09 | 3.5 | 71.3 | 39.1 | 22.5 |
| 实施例5 | Ir13 | 3.3 | 78.4 | 54.7 | 24.0 |
| 实施例6 | Ir17 | 3.3 | 79.3 | 56.9 | 24.1 |
| 实施例7 | Ir21 | 3.2 | 79.7 | 59.3 | 24.6 |
| 实施例8 | Ir25 | 3.8 | 65.1 | 33.4 | 20.6 |
| 实施例9 | Ir29 | 3.8 | 66.7 | 34.1 | 20.8 |
| 实施例10 | Ir33 | 3.7 | 68.1 | 35.3 | 21.2 |
| 实施例11 | Ir37 | 3.8 | 67.3 | 34.8 | 21.0 |
| 实施例12 | Ir41 | 3.8 | 69.2 | 35.9 | 21.3 |
| 实施例13 | Ir45 | 3.7 | 70.8 | 37.1 | 21.5 |
| 实施例14 | Ir49 | 4.0 | 65.8 | 33.4 | 20.7 |
| 实施例15 | Ir53 | 3.9 | 66.7 | 34.6 | 20.9 |
| 实施例16 | Ir57 | 3.8 | 67.5 | 35.9 | 21.4 |
| 实施例17 | Ir61 | 4.2 | 62.1 | 31.5 | 20.0 |
| 实施例18 | Ir65 | 4.1 | 63.4 | 32.7 | 20.7 |
| 实施例19 | Ir69 | 4.1 | 64.6 | 34.1 | 21.5 |
| 实施例20 | Ir73 | 3.9 | 66.9 | 38.6 | 23.2 |
| 实施例21 | Ir77 | 3.9 | 68.4 | 39.9 | 23.6 |
| 实施例22 | Ir81 | 3.8 | 69.8 | 41.6 | 23.9 |
| 实施例23 | Ir85 | 3.7 | 68.3 | 39.5 | 23.7 |
| 实施例24 | Ir89 | 3.6 | 69.2 | 40.1 | 23.9 |
| 实施例25 | Ir93 | 3.6 | 70.4 | 40.7 | 24.2 |
本发明提供的该类铱配合物可作为发光材料应用于OLEDs的发光层，通过设计优化化合物的结构，本发明达到了调控器件效率和寿命的目的。由表1结果可以看出，本发明所述铱配合物在器件性能方面表现优良。
以上所述的仅是本发明的实施方式，在此应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出改进，但这些均属于本发明的保护范围。
Claims (7)
1.一种铱配合物，其特征在于结构通式如下：
其中用于配位的基团R1代表取代或非取代的芳杂环基；
其中R2、R3相同或者不同，独立地选自C1-C10的烷基；
其中X1、X2相同或者不同，代表C或N。
2.如权利要求1所述的铱配合物，其特征在于其中R1代表任意位被H、C1-C10的烷基、C1-C10的烷氧基、卤素、被一个或多个相同或不同卤素取代的C1-C10的卤代烷基、羟基、氨基、硝基中的一种或几种取代的吡啶基、嘧啶基、异喹啉基、喹唑啉基、吡啶并嘧啶基、噻吩并嘧啶基、呋喃并嘧啶基。
3.如权利要求1所述的铱配合物，其特征在于其中R2、R3独立地选自甲基、乙基、丙基、异丙基、叔丁基、异丁基或异戊基。
4.如权利要求1所述的铱配合物，其特征在于其中R1代表任意位被H、C1-C6的烷基、C1-C6的烷氧基、卤素、被一个或多个相同或不同卤素取代的C1-C6的卤代烷基、羟基、氨基、硝基中的一种或几种取代的：
5.如权利要求1所述的铱配合物，其特征在于R1代表任意位被H、C1-C6的烷基、C1-C6的烷氧基、-CF3、-CCl3、-CBr3、-CH2CF3、-CH2CCl3、-CH2CBr3、卤素、羟基、氨基、硝基中的一种或几种取代的：
6.如权利要求1所述的铱配合物，其特征在于所述铱配合物选自：
7.如权利要求1-6任一项所述的铱配合物在在制备有机电致发光器件中的应用。
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