绿色磷光四配位氮杂环卡宾铜(Ⅰ)配合物的合成及发光性质
Syntheses and Luminescent Properties of Green Phosphorescent Four-Coordinated N-Heterocyclic Carbene Copper(Ⅰ) Complexes
作者单位E-mail
杨冰冰 江西科技师范大学有机功能分子研究所, 南昌 330013  
赵丰 江西科技师范大学有机功能分子研究所, 南昌 330013 zhf19752003@163.com 
许胜先 江西科技师范大学化学化工学院, 南昌 330013  
何海峰 江西科技师范大学化学化工学院, 南昌 330013  
摘要: 为了制备发光性能优良的新型四配位氮杂环卡宾铜(Ⅰ)配合物,以咪唑、苯并咪唑、2-溴-5-氟-6-甲基吡啶和溴化苄为初始原料,反应生成氮杂环卡宾配体(Ph-Im-flumePy)PF6和(Ph-BenIm-mePy)PF6,随后卡宾配体与Cu粉及配体双(2-二苯基膦)苯醚(POP)反应,制备出2个四配位类型的氮杂环卡宾铜(Ⅰ)配合物[Cu(Ph-Im-flumePy)(POP)]PF6P1)和[Cu(Ph-BenIm-flumePy)(POP)]PF6P2)。通过核磁、质谱技术对产物结构进行了表征。系统研究了配合物的紫外-可见吸收光谱、发射光谱以及发光寿命等光学特性。结果表明,配合物P1P2的最低吸收峰分别位于325和335 nm处。粉末状态下,配合物P1在514 nm处有较强的绿光发射,量子发光效率为82.6%,激发态寿命为56 μs;而配合物P2的波长在516 nm处,量子发光效率为49.2%,激发态寿命为50.6 μs。在PMMA(10%,w/w)膜片中,配合物P1的发射波长蓝移至505 nm处,激发态寿命为40.7 μs,量子发光效率为38.0%;而配合物P2的发射波长位于508 nm处,激发态寿命为61 μs,量子发光效率为44.2%。
关键词: 铜(Ⅰ)配合物  磷光材料  绿光发射  氮杂环卡宾
基金项目: 国家自然科学基金(No.21563013)和江西省自然科学基金(No.2010GZH0035)资助项目。
Abstract: N-heterocyclic carbene copper(Ⅰ) complexes have received great attention in organic light emitting diodes (OLEDs). However, a perusal of the literature shows that the three-coordinated species are widely studied, while studies on the luminescent properties of the four-coordinated NHC-Cu(Ⅰ) complexes is very scarce. With the aim of expanding this work, and motivated by the rich photophysical properties of the four-coordinated NHC-Cu(Ⅰ) complexes, we now present the preparation of the two four-coordinated NHC-Cu(Ⅰ) complexes. The N-heterocyclic carbene ligands, (Ph-Im-flumePy)PF6 and (Ph-BenIm-mePy)PF6, were synthesized by using imidazole, benzimidazole, benzyl bromide and 2-bromo-5-fluoro-6-methylpyridine as starting materials. Then the ligands were reacted with Cu powder and bis(2-diphenylphosphino)phenyl ether (POP) to synthesize the four-coordinated N-heterocyclic carbene copper(Ⅰ) complexes[Cu(Ph-Im-flumePy)(POP)]PF6 (P1) and[Cu(Ph-BenIm-flumePy)(POP)]PF6 (P2). The resulting complexes were characterized by 1H NMR and HRMS. The optical properties of the complexes were systematically investigated by measuring the UV-visible absorption spectra, luminescence spectra and phosphorescence lifetime of the complexes. The results show that the complex P1 and P2 displayed the lowest-absorption peak around at 325 and 335 nm, respectively. In the powder state, complex P1 exhibited strong green emission at 514 nm with 82.6% photoluminescence quantum yield (QY), as well as a 56 μs excited state lifetime at room temperature, while complex P2 showed the emission peak centered at 516 nm with the QY value of 49.2%, as well as the excited state lifetime of 50.6 μs. In the PMMA films (10%, w/w), complex P1 showed the emission wavelength at 505 nm and had the QY of 38.0% and the excited state lifetime of 40.7 μs, whereas complex P2 exhibited the strong green emission at 508 nm with the QY of 44.2% and the excited state lifetime of 61 μs.
Keywords: copper(Ⅰ) complex  phosphorescent material  green light emission  N-heterocyclic carbene
投稿时间:2019-01-07 修订日期:2019-03-29
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杨冰冰,赵丰,许胜先,何海峰.绿色磷光四配位氮杂环卡宾铜(Ⅰ)配合物的合成及发光性质[J].无机化学学报,2019,35(6):1020-1026.
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