| 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 |
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| 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）]PF6（P1）和[Cu（Ph-BenIm-flumePy）（POP）]PF6（P2）。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P1和P2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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