咔唑基铱(Ⅲ)磷光探针检测硝基芳烃及福井函数理论

Detection and Theoretical Study of Fukui Function of Nitroaromatics by Carbazole‑Based Iridium(Ⅲ)Phosphorescent Probe

将咔唑基团引入有机配体并利用2步法合成了室温下具有磷光发射的新型铱(Ⅲ)配合物Ir(ppyCz)_(3)。随后,以Ir(ppyCz)_(3)为发光探针用于开发1,3-二硝基苯等6种常见硝基芳烃的高效发光检测方案。研究表明,Ir(ppyCz)_(3)对1,3-二硝基苯具有最高的检测效率,猝灭常数K_(SV)为(26.38±1.05)L/mmol,最低检测限为2.50×10^(−6) mmol/L。密度泛函理论计算及光谱交叠实验表明,Ir(ppyCz)_(3)对硝基芳烃的发光检测机理为电子转移机理。硝基芳烃轨道权重福井函数的顺序与Ir(ppyCz)_(3)对硝基芳烃的检测效率顺序相符。

A room temperature phosphorescent Ir(Ⅲ)complex Ir(ppyCz)_(3) is synthesized by a two-step synthesis method with a carbazole modified organic ligand.The high-efficiency luminescent detection strategy of six familiar nitroaromatics including 1,3-dinitrobenzene,etc.is developed using Ir(ppyCz)_(3) as the luminescent probe.The highest detection efficiency of 1,3-dinitrobenzene by Ir(ppyCz)_(3) is demonstrated with the quenching content K_(SV) of(26.38±1.05)L/mmol,and minimum detection limit of 2.50×10^(−6) mmol/L.Density functional theory calculations and spectral overlap experiments show that the detection mechanism of Ir(ppyCz)_(3) for the six nitroaromatics is assigned to electron transfer.The sequence of the orbital weighted Fukui function for the six nitroaromatics dovetails with the corresponding detection efficiency sequence of nitroaromatics by Ir(ppyCz)_(3).