CN101974036A - 一种芴、螺芴取代的苯基吡啶铱配合物和制备方法及其应用 - Google Patents
一种芴、螺芴取代的苯基吡啶铱配合物和制备方法及其应用 Download PDFInfo
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Abstract
本发明属于有机电致发光材料领域,涉及一种含芴、螺芴取代的苯基吡啶铱配合物及其制备和应用,其制备方法是首先合成多种含芴、螺芴取代苯基吡啶类配体,然后将此类配体和三氯化铱水合物(IrCl3·3H2O)反应获得氯桥联二聚体中间体,再与乙酰丙酮在合适的溶剂中反应得到。本发明的铱配合物可以改变二齿配体中苯基的取代基的种类、位置,在一定范围内可调节发光波长,可广泛应用于有机电致发光领域。
Description
技术领域
本发明属于有机电致发光材料技术领域。具体而言,涉及铱配合物分子材料,尤其涉及一种以芴及螺二芴为取代基的苯基吡啶铱配合物和制备方法以及应用。
背景技术
有机电致发光材料与器件是当今国际前沿研究领域。目前,经过业界多年的努力,有机电致发光材料在部分照明,背光源等领域已经商品化。开发出来的有机显示器件已经在手机、MP3、音响显示面板等方面得到了应用。有机电致发光材料根据不同的发光原理可以分为荧光材料和磷光材料。和荧光材料相比,磷光材料由于可以充分利用包括单线态和三线态在内的所有能量形式,理论上可以使器件的内量子效率达到100%。其中,金属铱配合物是一类重要且被广泛研究的有机电致磷光材料([1]M.A.Baldo,S.Lamansky,P.E.Burrows,M.E.Thompon.S.R.Forrest.Appl.Phys.Lett.1999.75.4.[2]A.Tsuboyama,H.Iwawaki,M.Furugori,T.Mukaide,J.Kamatani,S.Igawa.T.Moriyama,S.Miura,T.Takiguchi.S.Okada,M.Hoshino,K.Ueno.J.Am.Chem.Soc.2003,125,12971.),由于金属铱配合物磷光寿命相对较短,量子效率高。因此,利用金属铱配合物作为发光材料成为提高器件效率的一种很好的手段。芴、螺芴引入金属铱配合物某种程度上增大了其体积,增大了发光层中铱与铱之间的距离,减少了浓度淬灭。同时芴、螺芴的引入,从浓度淬灭的根源入手,提高载流子传输能力,有效的使电荷分离,减少了激子的湮灭([3]陈金鑫,黄孝文;OLED有机电致发光材料与器件,清华大学出版社,2007)。金属铱配合物中有机配体的结构对发光效率和发射波长有很大的影响,因此设计合成新型的金属铱配合物,对开发不同颜色的磷光材料具有重要意义。
发明内容
本发明的目的是提供含有芴、螺芴取代的苯基吡啶铱配合物黄色电致磷光材料及其制备。本发明所合成的芴、螺芴取代的苯基吡啶铱配体,具有易于合成、成本低、易于修饰等优点。
本发明的技术方案是:把具有大的空间位阻的基团R引入到已有的铱配合物有机电致磷光材(ppy)Ir(acac)的配体中,增大了发光层中铱与铱之间的距离,减少了浓度淬灭。同时芴、螺芴取代基的引入,从浓度淬灭的根源入手,提高载流子传输能力,有效的使电荷分离,减少了激子的湮灭。所合成出的新型有机电致磷光材料的结构如下:
上述结构式中,R′为氢或烷氧基,R螺二芴或己基芴。
所述铱配合物的制备方法包括以下具体步骤:
a、由含9,9-二烷基取代芴基、螺芴取代的苯基吡啶类配体和化合物IrCl3·H2O在下述条件下反应获得氯桥二聚体:含9,9-二烷基取代芴基、螺芴取代的苯基吡啶类配体和化合物IrCl3·H2O的摩尔比为2.5∶1,反应温度为80~130℃,在氮气保护下反应时间为12~48小时,反应溶剂使用乙二醇二甲醚和水的混合溶液,乙二醇二甲醚和水的体积比为3∶1;反应溶剂与反应物的质量比为33~55∶1;
b、上述步骤得到的氯桥二聚体与乙酰丙酮在下述条件下反应得到权利要求1所述铱配合物:乙酰丙酮与所述氯桥联二聚体、碱性催化剂Na2CO3或K2CO3的摩尔比为3.5∶1∶7.9~28,在氮气保护下加热回流1~48小时,反应溶剂使用乙二醇甲醚;碱性催化剂、反应溶剂与反应物的质量比为1∶2.4~2.5∶75~108。
所述铱配合物的应用是:该配合物在制备有机电致发光器件中的应用。
本发明把具有大的空间位阻的基团R引入到已有的铱配合物有机电致磷光材(ppy)Ir(acac)的配体中,增大了发光层中铱与铱之间的距离,减少了浓度淬灭。同时芴、螺芴的引入,从浓度淬灭的根源入手,提高载流子传输能力,有效的使电荷分离,减少了激子的湮灭;并且具有易于合成、成本低、易于修饰等特点。本发明的铱配合物还可以改变二齿配体中苯基的取代基的种类、位置,在一定范围内可调节发光波长,可广泛应用于有机电致发光领域。
附图说明
图1为本发明苯基吡啶类配体的合成路线图
图2为本发明铱配合物合成路线图
具体实施方式
以下通过实施例对本发明作进一步详细阐述。
实施例1
1、二-[5-(9,9-二己基芴)-2-苯基吡啶]铱(乙酰丙酮)配合物6b的制备
(1)2-溴乙酰-9,9′-二己基芴2a的制备
在冰浴下,将溴乙酰溴(2.07ml,23.91mmol)滴加到己基芴(8g,23.91mmol)与AlCl3(3.83g,28.69mmol)的CH2Cl2溶液中,搅拌20min,然后放置室温搅拌1-2小时。倒入盐酸的冰浴中搅拌,CH2Cl2萃取,水洗,饱和Na2CO3水溶液洗,水洗,无水MgSO4干燥后减压浓缩,残余物经柱色谱(DCM∶PE=1∶4)层析得到黄色液体。1H NMR(CDCl3,500MHz)δ:8.02(d,J=6.6Hz,2H),7.81(m,2H),7.40(d,J=7.5Hz,3H),4.58(s,2H),2.07-2.02(m,4H),1.14-1.04(m,12H),0.79-0.77(m,6H),0.64-0.61(m,4H).13C NMR(CDCl3,125MHz)δ:191.23,152.07,151.25,146.96,139.43,132.38,128.76,128.60,127.09,126.08,123.23,123.07,122.63,120.88,119.68,55.32,40.12,31.30,29.56,23.67,23.52,22.51,13.98.
(2)3-苯基-6-(9,9′-二己基芴)-1,2,4-三嗪3b的制备
在250ml烧瓶中加入苯甲酰肼(7.4g,54.36mmol),溴乙酰9,9′-己基芴(12.38g,27.18mmol)、乙酸钠(2.68g,32.62mmol)、乙醇(82ml)、乙酸(35ml)。加入回流20小时,冷却,CH2Cl2萃取,水洗,饱和NaHCO3水溶液洗,水洗,MgSO4干燥后减压浓缩,残余物经柱色谱(DCM∶PE=1∶2)层析得到黄色固体3.5g,产率(28.56%)。熔点:92-94℃。1H NMR(CDCl3,500MHz)δ:9.14(s,1H),8.62-8.59(m,2H),8.29(s,1H),8.08(d,J=7.9Hz,1H),7.89(d,J=7.9Hz,1H),7.78(t,J=4.1Hz,1H),7.57(t,J=3.4Hz,3H),7.41-7.37(m,3H),2.06-2.03(m,4H),1.10-1.02(m,12H),0.76-0.73(m,6H),0.66-0.64(m,4H).13CNMR(CDCl3,125MHz)δ:162.02,155.25,152.05,151.42,146.47,144.09,139.94,134.71,131.61,131.53,128.90,128.06,128.03,126.97,125.34,123.01,121.07,120.34,55.43,40.34,31.46,29.64,23.76,22.53,13.95.
(3)2-苯基-5-(9,9′-二己基芴)吡啶4b的制备
3-苯基-6-(9,9′-二己基芴)-1,2,4-三嗪(1g,2.05mmol),二环[2.2.1]庚二烯(1.5ml),邻二氯苯(20ml)的混合物加热回流24-30小时,冷却,柱色谱(DCM∶PE=1∶1)层析给出白色固体0.7g,产率(70%)。熔点:89-90℃。1H NMR(CDCl3,500MHz)δ:9.02(s,1H),8.08(d,J=7.4Hz,2H),8.04(d,J=8.2Hz,1H),7.81(q,J=8.2Hz,2H),7.75(d,J=6.6Hz,1H),7.61(t,J=7.9Hz,2H),7.51(t,J=7.4Hz,2H),7.44(t,J=7.4Hz,1H),7.38-7.32(m,3H),2.04-2.00(m,4H),1.15-1.06(m,12H),0.77-0.75(m,6H),0.71-0.68(m,4H).13C NMR(CDCl3,125MHz)δ:155.83,151.70,150.95,148.15,141.16,140.37,139.03,136.24,135.38,135.01,128.91,128.78,127.32,126.83,126.78,125.76,122.89,121.21,120.29,120.22,119.86,55.17,40.34,31.43,29.66,23.77,22.54,13.98.
(4)二-[μ-氯-2-苯基-5-(9,9′-二己基芴)吡啶合铱]5b的制备
将2-苯基-5-(9,9′-二己基芴)吡啶(1.76g,3.61mmol)溶于乙二醇甲醚(75ml)加入IrCl3·H2O(0.45g,1.51mmol)、水(25ml),在氮气保护下,搅拌回流反应30小时,冷却到室温,CH2Cl2萃取,水洗,MgSO4干燥后减压浓缩,残余物经柱色谱(DCM∶PE=2∶1),正己烷重结晶得到橙黄色固体1.28,产率(58.8%)。1H NMR(CDCl3,500MHz)δ:9.96(s,4H),7.83(d,J=7.0Hz,4H),7.67(d,J=7.9Hz,4H),7.47-7.39(m,28H),7.10(d,J=8.0Hz,4H),6.77(t,J=7.2Hz,4H),6.58(t,J=7.0Hz,4H),6.01(d,J=7.7Hz,4H),2.23-2.06(m,16H),1.21-1.09(m,48H),0.83-0.75(m,40H).13CNMR(CDCl3,125MHz)δ:166.62,151.75,150.85,149.14,146.01,143.56,141.46,140.34,134.82,133.79,133.48,130.50,129.08,127.46,127.00,125.64,123.50,123.16,121.20,120.10,120.03,119.63,117.35,55.27,40.51,40.41,31.85,31.59,30.20,29.93,24.29,24.01,22.77,22.65,14.05.
(5)二-[5-(9,9′)-二己基芴-2-苯基吡啶]铱(乙酰丙酮)6b的制备
二[μ-氯-2-苯基-5-(9,9′-己基芴)吡啶合铱](1g,0.42mmol),乙酰丙酮溶于(0.12ml)的乙二醇二甲醚(40ml),加入K2CO3(0.46g,3.33mmol),氮气保护下回流8小时,冷却至室温,CH2Cl2萃取,水洗至中性,MgSO4干燥后减压浓缩,正己烷重结晶得到橙黄色固体0.94g,产率(89.8%)。1H NMR(CDCl3,500MHz)δ:8.93(s,2H),8.06(d,J=8.5Hz,2H),7.95(d,J=8.5Hz,2H),7.83(d,J=7.9Hz,2H),7.76(d,J=7.1Hz,2H),7.65-7.59(m,6H),7.39-7.33(m,6H),6.86(t,J=8.2Hz,2H),6.75(t,J=7.7Hz,2H),6.45(d,J=7.6Hz,2H),5.37(s,1H),2.04-2.01(m,8H),1.89(s,6H),1.12-1.06(m,24H),0.78-0.74(m,12H),0.73-0.60(m,8H).13CNMR(CDCl3,125MHz)δ:184.62,166.84,151.86,150.89,147.59,146.08,144.52,141.48,140.30,135.24,135.05,134.75,133.25,129.03,127.43,126.88,125.55,123.84,122.92,120.85,120.58,120.34,119.93,118.25,100.53,55.27,40.51,40.43,31.51,31.47,29.76,29.67,28.92,23.78,23.75,22.60,22.57,13.98.
实施例2
二-[5-(9,9′)-二己基芴-2-(4-甲氧基苯基)吡啶]铱(乙酰丙酮)6a的制备
(1)4-甲氧基苯甲酰肼1a的制备
在250ml的烧瓶中依次加入对甲氧基苯甲酸乙酯(11.4g)、85%水合肼(25ml)、甲醇(35ml),加热回流24小时,冷却析出白色固体,过滤,少量乙醇重结晶。熔点:139-141℃。1HNMR(CDCl3,500MHz)δ:9.61(s,1H),7.81(d,J=8.8Hz,2H),6.98(d,J=8.7Hz,2H),4.41(s,2H),3.79(s,3H).
(2)3-(4-甲氧苯基)-6-(9,9′-二己基芴)-1,2,4-三嗪3a的制备
在100ml烧瓶中加入对甲氧基苯甲酰肼(3.00g,18.04mmol)、2-溴乙酰-9,9′-二己基芴(4.11g,9.02mmol)、乙酸钠(0.88g,10.82mmol)、乙醇(35ml)、乙酸(15ml)。加入回流24小时,冷却,CH2Cl2萃取,水洗,饱和NaHCO3水溶液洗,水洗,MgSO4干燥后减压浓缩,残余物经柱色谱(DCM∶PE=3∶2)层析得到黄色固体1.9g,产率(40.5%)。熔点:137-139℃。1H NMR(CDCl3,500MHz)δ:9.07(s,1H),8.56(d,J=8.9Hz,2H),8.27(s,1H),8.04(d,J=7.9Hz,1H),7.86(d,J=7.9Hz,1H),7.77(q,J=4.6Hz,1H),7.39-7.35(m,3H),7.07(d,J=8.9Hz,2H),3.90(s,3H),2.07-2.02(m,4H),1.09-1.01(m,12H),0.75-0.72(m,6H),0.68-0.64(m,4H).13CNMR(CDCl3,125MHz)δ:162.50,161.79,154.59,151.99,151.39,146.39,143.84,140.00,131.81,129.76,127.98,127.25,126.94,125.13,123.00,120.91,120.29,114.29,55.41,40.34,31.46,29.65,23.76,22.54,13.96.
(3)2-(4-甲氧苯基)-5-(9,9′-二己基芴)吡啶4a的制备
2-(对甲氧基苯基)-5-(9,9′-二己基芴)-1,2,4-三嗪(2.35g,4.52mmol)、二环[2.2.1]庚二烯(4ml),邻二氯苯(40ml)的混合物加热回流24-30小时,冷却,柱色谱(DCM∶PE=1∶1)层析给出白色固体1.5g,产率(64%)。熔点:109-111℃。1H NMR(CDCl3,500MHz)δ:8.96(s,1H),8.03(d,J=8.7Hz,1H),7.99(d,J=8.3Hz,2H),7.80-7.72(m,3H),7.59(t,J=8.6Hz,2H),7.37-7.32(m,3H),7.04(d,J=8.7Hz,2H),3.89(s,3H),2.02-1.99(m,4H),1.12-1.02(m,12H),0.77-0.74(m,6H),0.69-0.67(m,4H).13CNMR(CDCl3,125MHz)δ:160.41,155.52,151.67,150.94,147.99,141.02,140.41,136.38,134.94,134.65,131.65,128.04,127.26,126.82,125.67,122.88,121.13,120.19,119.83,119.51,114.13,55.33,55.15,40.34,31.43,29.66,23.74,22.54,13.98.
(4)二-[μ-氯-2-(4-甲氧苯基)-5-(9,9’-二己基芴)吡啶合铱]5a的制备
将(1.25g,2.41mmol)2-对甲氧基苯基-5-(9,9′-己基芴)吡啶溶于乙二醇甲醚(30ml)加入IrCl3·H2O,(0.29g,0.96mmol)、水(10ml),在氮气保护下,搅拌回流反应30小时,冷却到室温,CH2Cl2萃取,水洗,MgSO4干燥后减压浓缩,残余物经柱色谱(DCM∶PE=1∶1),正己烷重结晶得到橙黄色固体0.99g,产率(90%)。1H NMR(CDCl3,500MHz)δ:9.83(s,4H),7.80(d,J=7.1Hz,4H),7.64(d,J=7.9Hz,4H),7.44(m,28H),7.04(d,J=7.9Hz,4H),6.37(d,J=8.4Hz,4H),5.51(s,4H),3.34(s,12H),2.18-1.99.(m,16H),1.21-1.09(m,48H),0.81-0.74(m,40H).13CNMR(CDCl3,125MHz)δ:166.40,159.72,151.73,150.88,148.93,148.17,141.14,140.44,137.72,136.76,135.16,133.98,132.51,127.36,126.98,125.51,124.85,123.19,120.01,119.67,116.67,114.94,107.54,55.23,54.36,40.47,40.42,31.84,31.64,30.21,30.00,24.31,24.05,22.79,22.70,14.05.
(5)二-[5-(9,9′-二己基芴)-2-(4-甲氧基苯基)吡啶]铱(乙酰丙酮)6a的制备
二-[μ-氯-2-(4-甲氧苯基)-5-(9,9’-二己基芴)吡啶合铱](0.73g,0.29mmol),乙酰丙酮溶于(0.1ml)的乙二醇二甲醚,加入K2CO3(0.32g,2.32mmol)。氮气保护下回流8小时,冷却至室温,CH2Cl2萃取,水洗至中性,MgSO4干燥后减压浓缩,正己烷重结晶得到橙黄色固体0.69g,产率(90%)。1H NMR(CDCl3,500MHz)δ:8.84(s,2H),8.01(d,J=8.5Hz,2H),7.80(d,J=8.6Hz,4H),7.75(d,J=7.3Hz,2H),7.61(d,J=8.0Hz,2H),7.65-7.59(m,6H),7.56(d,J=8.4Hz,4H),7.38-7.32(m,6H),6.46(d,J=8.6Hz,2H),5.35(s,1H),3.57(s,6H),2.02-1.99(m,8H),1.88(s,6H),1.12-1.05(m,24H),0.77-0.74(m,12H),0.73-0.61(m,8H).13CNMR(CDCl3,125MHz)δ:184.57,166.49,159.63,151.80,150.86,149.45,145.87,141.24,140.35,137.81,135.44,135.00,133.56,127.33,126.84,125.39,125.18,122.89,120.43,120.29,119.86,118.56,117.53,106.11,100.59,55.23,54.44,40.53,40.45,31.50,31.47,29.75,29.69,28.92,23.77,23.73,22.59,13.97.
实施例3
二-(5-(2-螺二芴基)-2-苯基吡啶)铱(乙酰丙酮)6c的制备
(1)2-溴乙酰螺二芴2b的制备
在250ml三口烧瓶中,将螺二芴(12g,37.97mmol)加入到AlCl3(6.08g,45.57mmol)的干燥的二氯甲烷溶液中去,在冰浴搅拌下将溴乙酰溴(7.66g,37.97mmol)的二氯甲烷(20ml)溶液慢慢滴加到三口烧瓶中,室温搅拌10小时后倒入盐酸的冰浴中搅拌,CH2Cl2萃取,水洗,饱和Na2CO3水溶液洗,水洗,MgSO4干燥后减压浓缩,残余物经柱色谱(DCM∶PE=2∶3)层析得到白色固体11.35g,产率(68.35%)。熔点:175-177℃。1H NMR(CDCl3,500MHz)δ:8.04(d,J=8.1Hz,1H),7.91(d,J=8.1Hz,2H),7.87(d,J=7.7Hz,2H),7.41-7.36(m,3H),7.35(s,1H),7.18(t,J=7.4Hz,1H),7.09(t,J=7.4Hz,2H),6.76(d,J=7.6Hz,1H),6.69(d,J=7.6Hz,2H),4.29(s,2H).13CNMR(CDCl3,125MHz)δ:190.58,150.21,149.53,147.47,141.87,140.03,133.32,129.55,129.42,128.12,127.99,124.59,124.31,123.91,121.15,120.30,120.16,65.83,31.45.(2)3-苯基-6-(2-螺二芴基)-1,2,4三嗪3c的制备
在250ml烧瓶中加入苯甲酰肼(5.77g,42.39mmol)、溴乙酰螺二芴(9.27g,21.20mmol)、乙酸钠(2.09g,25.44mmol)、乙醇(70ml)、乙酸(30ml)。加入回流20小时,冷却,CH2Cl2萃取,水洗,饱和NaHCO3水溶液洗,水洗,MgSO4干燥后减压浓缩,残余物经柱色谱(DCM∶PE=2∶1)层析得到黄色固体4.5g,产率(45%)。熔点:239-240℃。1H NMR(CDCl3,500MHz)δ:8.88(s,1H),8.51(d,J=6.4Hz,2H),8.21(d,J=8.0Hz,1H),8.05(d,J=8.0Hz,1H),7.94(d,J=7.6Hz,1H),7.89(d,J=7.7Hz,2H),7.59(s,1H),7.52(d,J=6.3Hz,3H),7.44-7.38(m,3H),7.19(t,J=7.5Hz,1H),7.13(t,J=7.5Hz,2H),6.79(t,J=7.9Hz,3H).13CNMR(CDCl3,125MHz)δ:161.93,154.65,150.23,149.51,147.94,146.28,144.56,141.87,140.60,134.53,132.54,131.52,128.84,128.00,127.94,126.37,124.25,123.97,122.33,120.83,120.64,120.23,65.98,53.45.
(3)2-苯基-5-(2-螺二芴基)吡啶4c的制备
在250ml烧瓶中,依次加入2-苯基-5-(2-螺二芴基)-1,2,4-三嗪(3.8g,8.06mmol)、邻二氯苯(40ml)、二环[2.2.1]庚二烯(3.5ml),加热回流24-30小时,冷却,柱色谱(CH2Cl2)层析给出白色固体3.05g,产率(80.6%)。熔点:239-241℃。1H NMR(CDCl3,500MHz)δ:8.77(s,1H),7.96(d,J=8.2Hz,3H),7.88(t,J=8.2Hz,3H),7.76(d,J=8.3Hz,1H),7.66(t,J=6.4Hz,2H),7.45(t,J=7.2Hz,2H),7.40(q,J=5.4Hz,4H),7.15(q,J=6.9Hz,3H),6.97(s,1H),6.78(q,J=7.6Hz,3H).13CNMR(CDCl3,125MHz)δ:155.83,149.89,149.06,148.42,147.95,141.75,141.07,138.88,137.17,134.89,134.61,128.89,128.72,128.14,127.90,127.85,126.72,126.61,124.07,122.47,120.60,120.20,120.07,120.05,66.02,55.43.
(4)二-[μ-氯-2-苯基-5-(2-螺二芴基)吡啶合铱]5c的制备
将入2-苯基-5-螺二芴吡啶(2.6g,5.32mmol)和化合物IrCl3·H2O(0.63g,2.13mmol),溶于(90ml)乙二醇甲醚、(30ml)水,在氮气保护下搅拌加热,回流反应24小时后,冷却至室温,CH2Cl2萃取,水洗至中性,MgSO4干燥后减压浓缩,残余物经柱色谱(DCM∶PE=3∶2)层析得到橙黄色固体1.4g,产率(56%)。1H NMR(CDCl3,500MHz)δ:9.35(s,4H),7.95(d,J=7.7Hz,4H),7.91(d,J=7.7Hz,8H),7.64(d,J=8.0Hz,4H),7.47(t,J=7.5Hz,4H),7.39(t,J=7.7Hz,8H),7.29(s,4H),7.25-7.16(m,12H),6.94(t,J=7.9Hz,8H),6.86(d,J=7.5Hz,4H),6.74-6.67(m,12H),6.55(d,J=7.7Hz,4H),6.46(t,J=7.8Hz,4H),6.39(s,4H),5.69(d,J=7.7Hz,4H).
(5)二-(5-(2-螺二芴基)-2-苯基吡啶)铱(乙酰丙酮)6c的制备
将二-[μ-氯-2-苯基-5-(2-螺二芴基)吡啶合铱](1g,0.43mmol)、乙酰丙酮(0.12g,1.2mmol)溶于40ml的乙二醇二甲醚,加入K2CO3(0.47g,3.41mmol),氮气保护下回流8小时,冷却至室温,抽滤,水洗,CH2Cl2洗涤,烘干得到橙黄色固体0.85g,产率(81%)。熔点大于320℃。
实施例4
二-(2-对甲氧基苯基-5-螺二芴吡啶)铱(乙酰丙酮)6d的制备
(1)3-(4-甲氧苯基)-6-螺二芴-1,2,4三嗪3d的制备
在250ml烧瓶中加入对甲氧基苯甲酰肼(7.60g,45.73mmol)、溴乙酰螺二芴(10g,22.86mmol)、乙酸钠(2.25g,27.44mmol)、乙醇(70ml)、乙酸(30ml)。加入回流24小时,冷却,CH2Cl2萃取,水洗,饱和NaHCO3水溶液洗,水洗,MgSO4干燥后减压浓缩,残余物经柱色谱(DCM∶PE=3∶1)层析得到黄色固体6.2g,产率(54.1%),熔点:294-296℃。1H NMR(CDCl3,500MHz)δ:8.83(s,1H),8.46(d,J=8.8Hz,2H),8.17(d,J=8.1Hz,1H),8.03(d,J=8.1Hz,1H),7.93(d,J=7.6Hz,1H),7.89(d,J=7.7Hz,2H),7.56(s,1H),7.43-7.37(m,3H),7.18(t,J=7.5Hz,1H),7.13(d,J=7.5Hz,2H),7.02(d,J=8.9Hz,2H),6.78(t,J=7.9Hz,3H),3.88(s,3H).13C NMR(CDCl3,125MHz)δ:162.46,161.71,154.00,150.18,149.47,147.97,146.20,144.31,141.86,140.65,132.72,129.73,128.74,127.96,127.91,127.08,126.14,124.22,123.96,122.15,120.76,120.57,120.19,114.22,65.95,55.39.
(2)2-(4-甲氧苯基)-5-螺二芴吡啶4d的制备
2-对甲氧基苯基5-螺二芴1,2,4-三嗪(5.1g,10.17mmol)、二环[2.2.1]庚二烯(6ml),邻二氯苯(60ml)的混合物加热回流24-30小时,冷却,柱色谱(CH2Cl2)层析给出白色固体4g,产率(78.7%)。熔点:275-277℃。1H NMR(CDCl3,500MHz)δ:8.73(s,1H),7.93(q,J=7.9Hz,3H),7.87(t,J=7.3Hz,3H),7.71(dd,J=8.8Hz,2.3Hz,2H),7.66(d,J=7.9Hz,1H),7.59(d,J=8.3Hz,1H),7.40-7.36(m,3H),7.14-7.10(m,3H),6.97(d,J=8.9Hz,3H),6.78-6.74(m,3H),3.84(s,3H).13CNMR(CDCl3,125MHz)δ:160.38,155.51,149.86,149.04,148.45,147.79,141.75,141.61,141.11,137.30,134.82,133.88,131.50,128.09,127.99,127.90,127.84,126.51,124.07,122.38,120.17,120.06,119.25,114.07,65.96,55.32.
(3)二-[μ-氯桥-2-(4-甲氧苯基)-5-螺二芴吡啶合铱]5d的制备
于250ml烧瓶中依次加入2-对甲氧基苯基-5-螺二芴吡啶(2.5g,5.00mmol),IrCl3·H2O(0.6g,2.01mmol),乙二醇甲醚(90ml)、水(30ml),在氮气保护下,回流24小时,冷却,CH2Cl2萃取,水洗至中性,MgSO4干燥后减压浓缩,残余物经柱色谱(DCM∶PE=3∶1),正己烷重结晶得到橙黄色固体1.3g,产率(53%)。1H NMR(CDCl3,500MHz)δ:9.23(s,4H),7.91(d,J=7.7Hz,4H),7.87(d,J=7.5Hz,8H),7.59(d,J=8.0Hz,4H),7.40(t,J=7.2Hz,4H),7.36(t,J=6.1Hz,8H),7.21-7.12(m,16H),7.09(d,J=8.6Hz,4H),6.94(t,J=7.5Hz,4H),6.88(d,J=8.1Hz,4H),6.81(d,J=7.5Hz,4H),6.67(d,J=7.4Hz,4H),6.53(d,J=7.8Hz,4H),6.34(s,4H),6.30(d,J=8.4Hz,4H),3.17(s,12H).13C NMR(CDCl3,125MHz)δ:166.48,159.57,149.47,148.71,148.63,148.53,148.20,141.74,141.57,140.68,136.33,136.06,134.79,132.45,128.23,127.91,127.74,126.95,123.92,123.87,123.77,121.25,120.39,116.90,113.77,107.93,66.05,54.28.
(4)二-(2-对甲氧基苯基-5-螺二芴吡啶)铱(乙酰丙酮)6d的制备
将二[μ-氯-2-(4-甲氧苯基)-5-螺二芴吡啶合铱](1g,0.41mmol)、乙酰丙酮(0.11g,1.1mmol)溶于40ml的乙二醇二甲醚,加入K2CO3(0.45g,3.26mmol),氮气保护下回流8小时,冷却至室温,CH2Cl2萃取,水洗至中性,MgSO4干燥后减压浓缩,正己烷重结晶得到橙黄色固体0.97g,产率(92%)。1H NMR(CDCl3,500MHz)δ:8.45(s,2H),7.94(d,J=7.9Hz,2H),7.87-7.83(m,6H),7.75(d,J=8.6Hz,2H),7.62-7.59(m,4H),7.41-7.32(m,8H),7.14-7.08(m,6H),6.92(s,2H),6.78(d,J=7.6Hz,4H),6.72(d,J=7.5Hz,2H),6.34(d,J=8.7Hz,2H),5.69(s,2H),4.85(s,1H),3.43(s,6H),1.34(s,6H).
Claims (3)
2.一种权利要求1所述铱配合物的制备方法,其特征在于该方法包括以下具体步骤:
a、由含9,9-二烷基取代芴基、螺芴取代的苯基吡啶类配体和化合物IrCl3·H2O在下述条件下反应获得氯桥二聚体:含9,9-二烷基取代芴基、螺芴取代的苯基吡啶类配体和化合物IrCl3·H2O的摩尔比为2.5∶1,反应温度为80~130℃,在氮气保护下反应时间为12~48小时,反应溶剂使用乙二醇二甲醚和水的混合溶液,乙二醇二甲醚和水的体积比为3∶1;反应溶剂与反应物的质量比为33~55∶1;
b、上述步骤得到的氯桥二聚体与乙酰丙酮在下述条件下反应得到权利要求1所述铱配合物:乙酰丙酮与所述氯桥联二聚体、碱性催化剂Na2CO3或K2CO3的摩尔比为3.5∶1∶7.9~28,在氮气保护下加热回流1~48小时,反应溶剂使用乙二醇甲醚;碱性催化剂、反应溶剂与反应物的质量比为1∶2.4~2.5∶75~108。
3.一种权利要求1所述铱配合物的应用,其特征在于该配合物在制备有机电致发光器件中的应用。
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