CN108358967A - 一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法 - Google Patents

一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法 Download PDF

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CN108358967A
CN108358967A CN201810209937.8A CN201810209937A CN108358967A CN 108358967 A CN108358967 A CN 108358967A CN 201810209937 A CN201810209937 A CN 201810209937A CN 108358967 A CN108358967 A CN 108358967A
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赵丰
苏青知
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Jiangxi Science and Technology Normal University
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    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
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Abstract

本发明公开一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法，本发明的磷光配合物P‑1由铜粉直接与配体络合得到，该材料具有工艺简便、设备简单、原料易得且成本低的优点。

Description

一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备 方法
技术领域
本发明涉及发光材料技术领域，主要涉及一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法。
背景技术
磷光过渡金属配合物作为发光层在有机发光二极管(OLED)显示技术中有着极为重要的作用，其较强的自选轨道耦合作用可以俘获单态激子和三态激子参与发光，从而使器件的发光效率得到大幅度提高。到目前为止，基于贵金属配合物(如铱、铂)的红、绿光OLED器件外量子效率已经可以达到20％左右，远超过传统荧光材料理论上5％的发光极限值。对于三基色发光显示过程而言，除红光和绿光外，蓝光的需求也是必不可少的。但对蓝光发光材料的获取，就目前广泛使用的d6和d8过渡金属配合物而言，则存在内在的缺点。蓝光的发射需要较大的能级带宽，这就意味着要升高发射态的3MLCT态，但不可避免的会导致位于上位的金属态(3MC)与3MLCT能级差的减小，使3MLCT态跃迁到3MC态的几率大大增加。3MC态一般为暗态(black states)，不发光，这样将导致较低的发光效率。
相比于其他贵金属配合物，铜配合物与他们有着类似的光物理和光化学特性，而且在自然界含量高、廉价、环境友好，具备工业化应用的基础。更重要的一点是，Cu(I)配合物核外电子构型为d10，这种全满的d轨道意味着限制其他贵金属发光效率的3MC态是不存在的，所以在设计合成高能量蓝光发光材料时，铜过渡金属配合物具有更大的发展空间。但铜原子较弱的自选轨道耦合和激发态结构松弛变形
(Jahn-Teller distorted)又降低了铜配合物的发光效率。近年来，混杂双配体类型[Cu(N^N)(POP)]+配合物显示了高的发光效率，为铜配合物的应用提供了好的应用前景。
发明内容
本发明的目的在于提供一种新的天蓝色磷光四配位氮杂环卡宾一价铜配合物的制备方法及其性能研究，通过Cu粉和配体溶液配位反应，方便且廉价地制备获得了发蓝光的Cu(Ⅰ)配合物发光材料，且稳定性较高。
本发明实现上述技术目的采用的技术方案为：
一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法：所述配合物发光材料的结构式为Cu(POP)(NHC-1)(PF6)，式中POP为电中性含P配体(2-二苯基磷苯基醚)式中(NHC-1)为氮杂环卡宾双齿配体，该配体为氮杂环卡宾与1,2,3三氮唑的结合体，其分子结构为：
所述一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法：所述配合物结构为：
一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法：具体制备方法为：将卡宾配体直接与铜粉及双齿膦配体在乙腈溶液中反应即得到离子型氮杂环卡宾一价铜配合物。
一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法，其特征在于：所述配合物在电致发光器件中的应用。
附图说明
图1为配合物[(NHC-BBT)Cu(POP)]+PF6 -的合成路线图；
图2为卡宾配体及配合物[(NHC-BBT)Cu(POP)]+PF6 -的紫外-可见吸收(UV-Vis)光谱图；
图3为配合物[(NHC-BBT)Cu(POP)]+PF6 -340纳米激发波长下PMMA膜片及粉末的荧光发射谱图；
图4为配合物[(NHC-BBT)Cu(POP)]+PF6 -的荧光寿命图。
具体实施方式
下面通过实施例来具体地说明本发明的配合物[(NHC-BBT)Cu(POP)]+PF6 -的制备方法，这些实施例仅对本发明进行说明，而不是对本发明进行限制。
实施例1
(1)氮杂环卡宾双齿配体前驱体L-1的合成：
合成反应路线如图1所示，将叠氮化钠(2.93g,45mmol,1.5当量)、溴化苄(5.13g,30mmol,1.0当量)加入100mL的烧瓶中，再加入二甲基亚砜30mL,室温下氮气保护反应4小时。待反应完全萃取，干燥，旋蒸除去溶剂，得到淡黄色油状液体，即为中间产物M-1，测得产率为90％。
将中间产物M-1(3.59g,27mmol,1.0当量)、3-溴丙炔(3.21g,27mmol,1.0当量)、碘化亚铜(0.05g,27mmol,10％当量)依次加入100mL圆底烧瓶中，再加入四氢呋喃30mL，氮气保护60℃下反应24小时。待反应冷却至室温，萃取，干燥，旋蒸浓缩析出固体，加入乙醚洗涤,得到棕黄色固体，即为1-苄基-4-溴甲基-1H-[1,2,3]三唑，测得产率为32％。1H NMR(400MHz,DMSO)δ8.25(s,1H),7.36(dt,J＝17.7,6.7Hz,5H),5.71–5.53(m,2H),4.74(s,2H).
将1-苄基-4-溴甲基-1H-[1,2,3]三唑(0.75g,3mmol,1.0当量)与1-苯基-1H-苯并咪唑(0.58g,3mmol,1.0当量)加入50mL圆底烧瓶中，再加入25mL甲苯，在110℃下反应12小时。冷却至室温将沉淀抽滤并用乙醚洗涤之后溶解于水中，将含有六氟磷酸铵(0.73g,4.5mmol,1.5当量)的水溶液倒入其中，搅拌得到白色沉淀。抽滤，烘干，即为前驱体P-1，测得产率为80％。1H NMR(400MHz,DMSO)δ10.30(s,1H),8.41(s,1H),8.20(s,1H),7.79(d,J＝28.3Hz,8H),7.34(d,J＝11.2Hz,5H),5.94(s,2H),5.64(s,2H)。
(2)一价铜配合物P-1的合成
将所得前驱体，双(2-苯基磷苯基)醚和铜粉加入到50mL的圆底烧瓶中，50℃下反应12小时。等反应结束后冷却至室温，用硅藻土过滤，旋蒸过滤后的溶液至5mL左右，加入70mL无水乙醚，过滤，得到黄色沉淀。乙醇重结晶后得到黄色沉淀，即为配合物P1。产率59％，1H NMR(400MHz,DMSO)δ8.27(s,1H),7.96(d,J＝8.1Hz,1H),7.38–7.28(m,15H),7.19(s,11H),7.07(d,J＝3.9Hz,3H),7.00–6.94(m,5H),6.87(d,J＝3.8Hz,5H),6.41(s,2H),5.50(s,2H),5.41(d,J＝30.3Hz,2H),4.38(t,J＝5.1Hz,1H)。
光物理性能：室温下，[(NHC-BBT)Cu(POP)]+PF6 -固体粉末样品的发射峰在523nm，发光量子产率为3.4％；样品在PMMA膜片的发射峰在482nm，发光量子产率为26.7％，发光寿命为18.52(μs)，见说明书附图3。

Claims (4)

1.一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法，其特征在于：所述配合物发光材料的结构式为Cu(POP)(NHC-1)(PF6)，式中POP为电中性含P配体(2-二苯基磷苯基醚)式中(NHC-1)为氮杂环卡宾双齿配体，该配体为氮杂环卡宾与1,2,3三氮唑的结合体，其分子结构式为：
2.根据权利要求1所述一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法，其特征在于：所述配合物结构为：
3.权利要求1所述的一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法,其特征在于：具体制备方法为：将卡宾配体直接与铜粉及双齿膦配体在乙腈溶液中反应即得到离子型氮杂环卡宾一价铜配合物。
4.权利要求1所述一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法，其特征在于：所述配合物在电致发光器件中的应用。
CN201810209937.8A 2018-03-14 2018-03-14 一种天蓝色磷光四配位氮杂环卡宾一价铜配合物及其制备方法 Pending CN108358967A (zh)

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Application publication date: 20180803