CN1321125C - 喹啉类氮杂环为配体的红光铱配合物及其应用 - Google Patents
喹啉类氮杂环为配体的红光铱配合物及其应用 Download PDFInfo
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- 229910052757 nitrogen Inorganic materials 0.000 title claims description 12
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
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Abstract
本发明涉及基于喹啉类氮杂环为配体的铱配合物及其制备方法和作为红光材料在有机电致发光器件中的应用。选择一系列喹啉类氮杂环作为配体，与铱(III)配位，形成铱(III)配合物；并且通过真空蒸镀或溶液旋涂的方法将铱(III)配合物掺杂在主体材料中，构造多层器件或单层器件，实现高效红光发射。与其它的红光配体相比较，喹啉类配体具有合成和提纯容易等特点，而且相应的配合物保持了较短的寿命和较高的效率，为构造高效电致发光器件提供了可能性。
Description
技术领域
本发明涉及基于喹啉类氮杂环为配体的铱配合物和作为红光材料在有机电致发光器件中的应用。
技术背景
1987年C.W.Tang等人首次报导了八羟基喹啉铝(Alq3)的电致发光现象以来，有机发光二极管的研究引起了学术界和产业界的广泛兴趣。根据自旋统计理论，在多数有机发光二极管中，生成的单线态激子与三线态激子的比例为1∶3。三线态激子由于长的寿命和自旋禁阻的本质而表现为非辐射衰减，从而限制了器件的内量子效率不能超过25％。而过渡金属配合物由于金属原子的重原子效应，导致了很强的自旋一轨道偶合作用，从而增加了有效的单线态到三线态之间的系间窜越，即利用过渡金属配合物作为电致发光材料可以充分利用包括单线态和三线态在内的所有能量形式，大幅度提高器件的效率，理论上可使器件的内量子效率达到100％。
目前用作电致发光材料的过渡金属配合物主要有Ir(III)、Pt(II)、Os(II)、Re(I)、Cu(I)等重金属配合物.其中铱配合物由于具有较短的寿命和较高的效率而广泛应用于电致发光器件中，并已实现了红绿蓝三基色发光。
铱配合物的发光颜色强烈依赖于配体的结构，因此，我们可以选择适当的配体来调节发光颜色。目前，铱配合物中用于获得高效红光的配体主要有2-(2-苯并噻吩基)吡啶和1-苯基异喹啉等。这些配体的合成方法复杂，且不容易大量合成。因此，需要设计合成和提纯相对容易的配体用于高效的红光铱配合物。
发明内容
本发明的目的是提供一种基于喹啉类氮杂环为配体的红光铱配合物电致发光材料。
本发明设计并合成了一系列喹啉类氮杂环作为配体，与铱(III)配位，形成配合物；并且通过真空蒸镀或溶液旋涂的方法将铱(III)配合物掺杂在主体材料中，构造多层器件或单层器件，实现高效红光发射。与其它的红光配体相比较，喹啉类配体具有合成和提纯容易等特点，而且相应的配合物保持了较短的寿命和较高的效率，为构造高效电致发光器件提供了可能性。
本发明合成的铱(III)配合物均为单核六配位结构，具有如下基本结构：
结构通式中
代表以碳和氮为配位原子的二齿配体，具有如下结构：
其中，R1选自氢、氟、三氟甲基、氰基、C1-C30的烷基、C1-C20的烷氧基、C6-C30的芳基、C6-C30稠合的芳环基、C2-C30的杂芳基；Ar1选自以下芳香结构单元中的一种：
其中R2、R4、R6为C1-C30的烷基；R5为己基或辛基；R3为任意取代位置的C1-C30的烷基或C1-C20的烷氧基；R7选自氢、C1-C30的烷基、C1-C20的烷氧基、C6-C30的芳基；R8为C1-C30的烷基或C1-C20的烷氧基；X为氧或硫原子。
本发明上述的配合物，Ar1优先选自以下稠环芳香结构单元中的一种：
R3为任意取代位置的C1-C30的烷基或C1-C20的烷氧基
本发明上述的配合物，具有如下结构：
本发明上述的配合物，具有如下结构：
所有的喹啉类配体均通过Friedlnder反应制备。该反应以浓H2SO4为催化剂，以冰HAc为溶剂，回流反应16-24小时。所得产品用重结晶或柱分离提纯。
所有的铱(III)配合物均通过两步反应制得。首先，
配体与三氯化铱反应生成含氯桥的中间体；然后，氯桥被乙酰丙酮(acac)取代生成铱(III)配合物。
按照本发明，一种有机电致发光器件，具有在第一电极和第二电极之间形成的一层或多层有机薄层，其中至少一层有机层包括如本发明上述的一种或多种配合物
电致发光器件的发光层可以采用真空共蒸镀的方法制备，工艺如下：将铱(III)配合物和小分子主体材料在真空条件下同时蒸镀，通过两个独立的石英晶体震荡器来控制各自的蒸发速率，从而控制两者的含量。同时通过真空蒸镀法在阳极ITO和发光层之间引入空穴传输层，在金属阴极和发光层之间引入一到二层具有空穴阻挡或电子传输功能的有机小分子层，构造多层器件。用作主体材料的小分子包括4，4’-N，N’-二咔唑联苯(CBP)、2-(4-二苯基)-5-(4-叔丁基苯基)-1，3，4-噁二唑(PBD)、1，3，5-三(2-N-苯基苯并咪唑基)苯(TPBI)、3-(4-二苯基)-5-(4-叔丁基苯基)-4-(4-乙基苯基)-1，2，4-三唑(TAZ)等。在发光层中，铱(III)配合物与主体材料的重量比为1-9∶100。
电致发光器件的发光层也可以采用溶液旋涂的方法制备，工艺如下：将铱(III)配合物和高分子主体材料共混，溶解于氯仿CHCl3中，旋涂在经聚噻吩衍生物(PEDOT)修饰或未经其修饰的ITO玻璃表面，制备成发光层。用作主体材料的高分子包括：聚苯乙烯撑、聚苯撑、聚乙烯基咔唑、聚咔唑、聚芴或聚芴的衍生物。铱(III)配合物与高分子主体材料的重量比为1-9∶100。此外，发光层中还可以进一步掺入小分子载流子传输材料：2-(4-二苯基)-5-(4-叔丁基苯基)-1，3，4-噁二唑(PBD)、1，3，5-三(2-N-苯基苯并咪唑基)苯(TPBI)、3-(4-二苯基)-5-(4-叔丁基苯基)-4-(4-乙基苯基)-1，2，4-三唑(TAZ)、N，N’-双(3-甲基苯基)-N，N’-二苯基-1，1’-二苯基-4，4’-二胺(TPD)、或N，N’-二(1-萘基)-N，N’-二苯基-1，1’-二苯基-4，4’-二胺(NPB)。在器件组装上，旋涂完发光层后可直接蒸镀金属电极，制成单层器件；也可用真空蒸镀法在金属电极与发光层之间进一步引入一至两层具有空穴阻挡或电子传输功能的有机小分子层，构造多层器件。
附图说明
结合附图，通过示例性实施例的详细描述将会更清楚的理解本发明，其中：
图1给出化合物(1-NAPQ)2Ir(acac)和(TPAPQ)2Ir(acac)在二氯甲烷溶液中的紫外可见吸收(UV-Vib)光谱和光致发光(PL)荧光谱；
图2给出实施例2制造的有机EL器件的亮度-电压曲线；
图3给出实施例2制造的有机EL器件的发光效率和功率效率随亮度的变化曲线；
图4给出实施例1和2制造的有机EL器件的EL谱
具体实施方式
参考以下实施例详细描述本发明，以下实施例是说明性目的且不打算限制本发明的范围。
<反应式1>
合成实施例1：配合物(1-NAPQ)2Ir(acac)的合成
(1)配体1-NAPQ的合成
将1.97g(10mmol)邻氨基二苯甲酮和1.70g(10mmol)1-萘乙酮溶于15ml冰醋酸中，缓慢滴加0.1ml浓硫酸，搅拌，加热回流。反应18小时后，冷却到室温。反应混合物缓慢倒入40ml水和15ml浓氨水组成的混合溶液中。析出的沉淀发粘，用二氯甲烷萃取，反复水洗，无水Na2SO4干燥，过滤，旋转蒸发掉溶剂，柱分离提纯，得到2.85g产物(产率86％)。
(2)氯桥二聚体的合成
取1.46g(4.4mmol)配体1-NAPQ和0.705g(2mmol)IrCl3·3H2O加入50ml圆底烧瓶中，再加入乙二醇独乙醚30ml，蒸馏水10ml，反复换气3次，在氩气保护下搅拌加热，升温至130～140℃，回流反应36h后，过滤，得到的沉淀以乙醇和蒸馏水洗涤，干燥，柱分离提纯，得二聚体1.28g(产率72％)
(3)配合物(1-NAPQ)2Ir(acac)的合成
取二聚体0.89g(0.5mmol)，乙酰丙酮(acac)0.20g(2mmol)，无水碳酸钠0.53g(5mmol)，乙二醇独甲醚30ml，加入50ml圆底烧瓶中，反复换气3次，在氩气保护下搅拌加热，升温至130～140℃，回流反应24h后，过滤，所得固体使用混合溶剂(石油醚/二氯甲烷＝2/1)进行柱层析分离，得到最终产品500毫克。(产率53％)
(4)配合物(1-NAPQ)2Ir(acac)的结构分析
通过NMR和元素分析确定了该化合物的结构。
1H NMR(300MHz，CDCl3)：δ1.54(s，6H)，4.60(s，1H)，6.88(d，J＝8.2Hz，2H)，7.04(d，J＝8.4Hz，2H)，7.29(t，J＝7.4Hz，2H)，7.37-7.40(m，4H)，7.50(t，J＝7.6Hz，2H)，7.56-7.75(m，12H)，7.85(d，J＝7.2Hz，2H)，8.38(d，J＝8.6Hz，2H)，8.62(s，2H)，8.72(d，J＝8.5Hz，2H).
理论值(C55H39N2O2Ir)：C，69.38；H，4.13；N，2.94.实测值：C，69.30；H，4.38；N，2.69.
<反应式2>
合成实施例2：配合物(TPAPQ)2Ir(acac)的合成
合成方法与合成实施例1类似。
(1)配体TPAPQ的合成
将1.97g(10mmol)邻氨基二苯甲酮和2.87g(10mmol)4-二苯氨基苯乙酮溶于15ml冰醋酸中，缓慢滴加0.1ml浓硫酸，搅拌，加热回流。反应20小时后，冷却到室温。反应混合物缓慢倒入40ml水和15ml浓氨水组成的混合溶液中。析出的沉淀发粘，用二氯甲烷萃取，反复水洗，无水Na2SO4干燥，过滤，旋转蒸发掉溶剂，柱分离提纯，得到3.59g产物(产率80％)。
(2)氯桥二聚体的合成
取1.97g(4.4mmol)配体1-NAPQ和0.705g(2mmol)IrCl3·3H2O加入50ml圆底烧瓶中，再加入乙二醇独乙醚30ml，蒸馏水10ml，反复换气3次，在氩气保护下搅拌加热，升温至130～140℃，回流反应48h后，过滤，得到的沉淀以乙醇和蒸馏水洗涤，干燥，柱分离提纯，得二聚体1.46g(产率65％)
(3)配合物(TPAPQ)2Ir(acac)的合成
取二聚体1.12g(0.5mmol)，乙酰丙酮(acac)0.20g(2.0mmol)无水碳酸钠0.53g(5mmol)，乙二醇独甲醚30ml，加入50ml圆底烧瓶中，反复换气3次，在氩气保护下搅拌加热，升温至130～140℃，回流反应24h后，过滤，所得固体柱分离提纯，得到最终产品530毫克(产率45％)。
(4)配合物(TPAPQ)2Ir(acac)的结构分析
通过NMR和元素分析确定了该化合物的结构。
1H NMR(300MHz，CDCl3)：δ1.62(s，6H)，4.77(s，1H)，6.25(d，J＝2.1Hz，2H)，6.55(dd，J＝8.5，2.0Hz，2H)，6.80-6.91(m，20H)，7.42-7.59(m，16H)，7.68(s，2H)，7.74(d，J＝8.1Hz，2H)，8.58(d，J＝8.6Hz，2H)
理论值(C71H53N4O2Ir)：C，71.88；H，4.50；N，4.72.实测值：C，71.10；H，4.49；N，4.52.
实施例1：
对于给出的实施例，使用配合物(1-NAPQ)2Ir(acac)掺杂在CBP主体材料中制造有机EL器件。首先，在涂覆有ITO玻璃的表面蒸镀50nm的N，N’-二(1-萘基)-N，N’-二苯基-1，1’-二苯基-4，4’-二胺(NPB)作为空穴传输层。然后，在空穴传输层上沉积CBP形成30nm的发光层，其中掺杂3％的(1-NAPQ)2Ir(acac)。最后，依次沉积上空穴阻挡层(BCP：10nm)，电子传输层(Alq3：40nm)，界面层(LiF：1nm)和阴极(Al：100nm)。
所得的EL器件在100cd/m2的亮度下，发光效率为2.2cd/A，外量子效率为3.0％，发射峰在642nm，半峰宽为35nm，色坐标CIE值x＝0.71，y＝0.29。
实施例2：
对于该实施例，使用配合物(TPAPQ)2Ir(acac)掺杂在CBP主体材料中制造有机EL器件。首先，在涂覆有ITO玻璃的表面蒸镀50nm的N，N’-二(1-萘基)-N，N’-二苯基-1，1’-二苯基-4，4’-二胺(NPB)作为空穴传输层。然后，在空穴传输层上沉积CBP形成30nm的发光层，其中掺杂7％的(TPAPQ)2Ir(acac)。最后，依次沉积上空穴阻挡层(BCP：10nm)，电子传输层(Alq3：40nm)，界面层(LiF：1nm)和阴极(Al：100nm)。
所得的EL器件在100cd/m2的亮度下，发光效率为12.2cd/A，外量子效率为9.0％，发射峰在616nm，半峰宽为48nm，色坐标CIE值x＝0.67，y＝0.32。
Claims (5)
1.一种喹啉类氮杂环为配体的红光铱配合物，具有如下基本结构：
结构通式中
代表以碳和氮为配位原子的二齿配体，具有如下结构：
其中，R1选自氢、氟、三氟甲基、氰基、C1-C30的烷基、C1-C20的烷氧基、C6-C30的芳基、C6-C30稠合的芳环基、C2-C30的杂芳基；Ar1选自以下芳香结构单元中的一种：
其中R2、R4、R6为C1-C30的烷基；R5为己基或辛基；R3为任意取代位置的C1-C30的烷基或C1-C20的烷氧基；R7选自氢、C1-C30的烷基、C1-C20的烷氧基、C6-C30的芳基；R8为C1-C30的烷基或C1-C20的烷氧基；X为氧或硫原子。
2.一种有机电致发光器件，具有在第一电极和第二电极之间形成的一层或多层有机薄层，其中至少一层有机层包括如权利要求1的一种或多种配合物。
3.如权利要求1的配合物，Ar1优先选自以下稠环芳香结构单元中的一种：
R3为任意取代位置的C1-C30的烷基或C1-C20的烷氧基。
4.如权利要求1的配合物，具有如下结构：
5.如权利要求1的配合物，具有如下结构：
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