Influence of the central atom on the electronic properties of Lindqvist polyoxometalates

► The central atom role in Lindqvist polyoxomolybdates on their properties is studied by DFT method. ► The bond lengths between Mo and central atom, bridge and terminal atom increase with the increasing central atom size. ► The central atom size determines the oxidized capacity of anion with the central atom in the same group. ► The charge of central atom determines the RE value of the anion as the anion charge are dominated by the central atom. ► The nucleophilicity of bridge and terminal oxygen in hexamolybdate increases with X = O, to S and Se or X = N, to P and As.