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In this study, the structurally similar multinuclear cobaloxime complexes based on dioxime ligands were synthesized and characterized as trinuclear complexes with respect to varied axial groups. The multinuclear cobaloxime complexes were characterized by 1 H, 13 C-NMR, FT-IR, UV-Vis, LC-MS spectra, melting point and magnetic susceptibility measurements. These multinuclear cobaloxime complexes have been successfully applied to the synthesis of cyclic carbonates from CO 2 and epoxides under optimized conditions and without using any solvent. All multinuclear cobaloxime complexes obtained by click chemistry are good catalysts for the cycloaddition of CO 2 to different epoxides in the presence of pyridine as a co-catalyst. Additionally, the effects of epoxides, bases, temperature, pressure, and time on the yield of cyclic carbonates were investigated.