两种嘧啶基噻吩类磷光铱配合物的合成及表征

Synthesis and characterization of two pyrimidinyl thiophene-based phosphorescent iridium complexes

以2-嘧啶基噻吩(pymbt,L1)和2-嘧啶基苯并噻吩(pymbtp,L2)作为环金属化主配体,二(二苯基磷酰)亚胺(Htpip)作为O^O型辅助配体,合成了两种新型磷光金属铱配合物(pymbt)_(2)Ir(tpip)(Ir1)和(pymbtp)_(2)Ir(tpip)(Ir2)。通过核磁共振氢谱、质谱和元素分析对其进行了结构表征,用紫外-可见吸收光谱和荧光发射光谱进行了光物理性质的研究。结果表明,铱配合物Ir1和Ir2在溶液中的最大发射峰分别为563 nm和619 nm,为橙黄光和红光。在无水无氧二氯甲烷溶液中相对量子效率分别为6.3%和10.1%,磷光寿命为0.50μs和0.63μs。同时采用含时密度泛函理论(TDDFT)对配合物Ir1和Ir2的最低能量电子跃迁进行了计算,结果与实验测得的相应光谱数据对应的趋势相符。

Using 2-pyrimidinyl thiophene(pymbt,L1),2-pyrimidinyl benzothiophene(pymbtp,L2)as the cyclometalated main ligands and tetraphenylimidodiphosphinate(Htpip)as the O^O ancillary ligand,two novel phosphorescent iridium complexes(pymbt)_(2)Ir(tpip)(Ir1)and(pymbtp)_(2)Ir(tpip)(Ir2)were synthesized.Their structures were characterized by^(1)H-NMR,MS and elemental analysis method.Their photophysical properties were studied by UV-Vis absorption and photoluminescence spectra.The results show that the maximum emission peaks of iridium(Ⅲ)complexes Ir1 and Ir2 in CH_(2)Cl_(2)solution are 563 nm and 619 nm,respectively,corresponding to orange and red light emission.In anhydrous and oxygen-free CH_(2)Cl_(2)solution,the relative quantum efficiencies are 6.3%and 10.1%,respectively,and the corresponding phosphorescence lifetime is 0.50μs and 0.63μs.The lowest energy electronic transitions of complexes Ir1 and Ir2 were calculated by time-dependent density functional theory(TDDFT),and the results are consistent with the corresponding trend in the experimental spectra.