Abstract: | Self‐assembly of a resorcin[4]arene‐based ligand (TMR4A) with metal salts and H3PMo12O40·xH2O offers two isostructural complexes, namely, [Ni2Cl(TMR4A)2(CH3CN)2]·[PMo12O40]·4CH3CN ( 1 ) and [Co2Cl(TMR4A)2(CH3CN)2]·[PMo12O40]·4CH3CN ( 2 ). In both 1 and 2 , one Cl? anion bridges two metal cations, and each metal cation is further chelated by four 2‐mercaptopyridine N‐oxide groups of one TMR4A, producing a [M2Cl(TMR4A)2]3+ dimer (M = Ni or Co). The negative [PMo12O40]3? as a counter‐anion balances the positive charge. Markedly, 1 and 2 exhibit high stability in aqueous solutions with different pH values and in organic solvents. Remarkably, the efficient heterogeneous catalytic capability for oxidative desulfurization was studied by suing 1 and 2 as recycled catalysts. Moreover, the electrochemical behaviors of the two compounds were discussed as well. |