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335nm处。粉末状态下,配合物P1在514nm处有较强的绿光发射,量子发光效率为82.6%,激发态寿命为56μs;而配合物P2的波长在516nm处,量子发光效率为49.2%,激发态寿命为50.6μs。在PMMA(10%,w/w)膜片中,配合物P1的发射波长蓝移至505nm处,激发态寿命为40.7μs,量子发光效率为38.0%;而配合物P2的发射波长位于508nm处,激发态寿命为61μs,量子发光效率为44.2%。
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.
作者
杨冰冰
赵丰
许胜先
何海峰
YANG Bing-Bing;ZHAO Feng;XU Sheng-Xian;HE Hai-Feng(Jiangxi Key Laboratory of Organic Chemistry,Jiangxi Science and Technology Normal University,Nanchang 330013,China;School of Chemistry and Chemical Engineering,Jiangxi Science and Technology Normal University,Nanchang 330013,China)
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
2019年第6期1020-1026,共7页
Chinese Journal of Inorganic Chemistry
基金
国家自然科学基金(No.21563013)
江西省自然科学基金(No.2010GZH0035)资助项目
关键词
铜(Ⅰ)配合物
磷光材料
绿光发射
氮杂环卡宾
copper(Ⅰ) complex
phosphorescent material
green light emission
N-heterocyclic carbene
