Self-supplying coreactant radical and structural distortion induced by carbonate ligand in metal-organic framework for anomalous deep-red Self-electrochemiluminescence

金属有机框架中碳酸盐配体诱导的自供共反应自由基和结构畸变导致异常深红色自电化学发光

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Abstract

Self-electrochemiluminescence (self-ECL) can deal with the problems of limited electron transport efficiency, reduced signal stability, and redundant ECL processes. A feasible solution is to assemble the luminescent components and coreactant radicals together. Here a self-ECL material was designed relying on a europium-based metal-organic framework (Eu-MOF, ZL-2) with 1,10-phenanthroline and CO(3) (2-) as ligands under strong alkaline conditions. Upon oxidation of the CO(3) (2-) ligand to produce C(2)O(6) (2-), OH˙ could be generated to act as a coreactant radical, which reacted with the luminophore radical of oxidized ZL-2 to realize self-ECL without an extra coreactant. The coordination of the CO(3) (2-) ligand induced Eu(3+) to occupy some sites in the tetrakaidecahedron structure of ZL-2, which caused the structure to distort, and thus triggered the unusual electric-dipole transfer transition (5)D(0)-(7)F(4). Therefore, ZL-2 was endowed with deep-red luminescence in the first near-infrared (NIR-I) region, which filled a gap in self-NIR-ECL applications. This discovery suggested a novel promising dual-function mechanism of the CO(3) (2-) ligand, undoubtedly broadening the application and development of MOFs in the ECL field.

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