用于高效检测 2,4,6-三硝基苯酚和氧的 AIPE-活性阳离子 Ir(III) 配合物。

AIPE-active cationic Ir(III) complexes for efficient detection of 2,4,6-trinitrophenol and oxygen.

机构信息

State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China.

School of Environmental Science and Technology, Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), Dalian University of Technology, Dalian 116024, China.

出版信息

Dalton Trans. 2022 Dec 20;52(1):128-135. doi: 10.1039/d2dt03537e.

DOI:10.1039/d2dt03537e

PMID:36468630

Abstract

A cationic Ir(III) complex, Ir2, with a diphenylamino (DPA)-substituted 2-phenylbenzothiazole derivative as the cyclometalating ligand was designed and synthesized. Ir2 shows obvious aggregation-induced phosphorescent emission (AIPE) in HO/CHCN, compared with a non-DPA-substituted Ir1. The AIPE-active Ir2 demonstrates efficient detection of 2,4,6-trinitrophenol, providing a higher quenching constant ( = 2 644 330 M. 73 583 M for Ir1) and a lower limit of detection (LOD = 2.23 nM . 50.17 nM for Ir1). High-resolution mass spectrometry analysis and density functional theory calculations demonstrate that photoinduced electron transfer may be responsible for the emission quenching. Immobilized in an ethyl cellulose film, Ir2 exhibits high oxygen sensitivity (appSV = 0.0572 Torr. 0.0090 Torr for Ir1) and excellent reversibility in 10 cycles. This work reveals that the DPA group plays an important role in tuning the AIPE properties and increasing the performances of the luminescent probes.

摘要

一种具有二苯基氨基（DPA）取代的 2-苯基苯并噻唑衍生物作为环金属化配体的阳离子 Ir(III) 配合物 Ir2 被设计和合成。与非 DPA 取代的 Ir1 相比，Ir2 在 HO/CHCN 中表现出明显的聚集诱导磷光发射（AIPE）。AIPE 活性 Ir2 对 2,4,6-三硝基苯酚具有高效检测能力，提供了更高的猝灭常数（ = 2644330 M.73583 M ，Ir1 为 50.17 nM）。高分辨率质谱分析和密度泛函理论计算表明，光诱导电子转移可能是导致发射猝灭的原因。固定在乙基纤维素膜中，Ir2 表现出高的氧灵敏度（appSV = 0.0572 Torr.0.0090 Torr，Ir1 为 10 个循环）和优异的可逆性。这项工作表明，DPA 基团在调节 AIPE 性质和提高发光探针性能方面发挥着重要作用。