Assembly of AgStBu and PhCOOH ligands with the assistance of soluble silver salt CH3COOAg/CF3SO3Ag in methanol, N, N-dimethylformamide (DMF) and dichloromethane solution, yielded two Ag20 cage isomers co-constructed by thiol and carboxylate/sulfonate ligand encapsulating a CO32– anion template, [(CO32–)@Ag20(StBu)10(PhCOO)4(CH3COO)4(DMF)4] (1) and [(CO32–)@Ag20(StBu)10(PhCOO)6(CF3SO3)2(DMF)4]·2DMF (2). The CO32– anion template was generated in situ by fixing atmospheric CO2. The precise structures of 1 and 2 were confirmed by single-crystal X-ray diffractometry (SCXRD). The thermal stability of compounds 1 and 2 was proved by thermogravimetric (TG) analysis, and their solution stability was characterized by nuclear magnetic resonance hydrogen spectroscopy (1H NMR). The absorption spectra, photocurrent responses, and luminescence of compounds 1 and 2 were investigated. In addition, the photodegradation of methylene blue (MB) and cyclic voltammetry characteristic curves of 1 and 2 were also studied
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