To understand the substituting effects of imidazole ring on the reaction equilibrium,the interactions between diperoxovanadate complex NH_4[OV(O_2)_2{2-(2'-Pyridine)-Imidazole}]·4H_2O (abbr.bpV(Imi-Py)) and a series of imidazole-like ligands (imidazole,2-methyl-imidazole,4-methyl-imidazole,and histidine) in solution were explored using multinuclear (~1H,~(13)C,and ~(51)V) magnetic resonance,diffusion ordered spectroscopy (DOSY),and variable temperature NMR in 0.15 mol·L~(-1) NaCl ionic medium for mimicking the physiological conditions.The experimental results indicated that the activities of bpV(Imi-Py) and organic ligands were as follows:imidazole≈4-methyl-imidazole2-methyl- imidazolehistidine.The stedc effect of the organic ligands affects the reaction equilibrium.At the same time,new six- coordinated peroxovanadate species [OV(O_2)_2L]-(L=imidazole-like ligands) were formed due to the competitive coordination between 2-(2'-pyridyl)-imidazole and the imidazole-like ligands.When the ligand was 4-methyl- imidazole or histidine,a pair of isomers was formed.