A DFT study on the electronic and redox properties of [PW11O39(ReN)]n-(n=3, 4, 5) and [PW11O39(OsN)]2-

DFT calculations were carried out to investigate the electronic and redox properties of nitrido-functionalized polyoxometalate species, [PW11O39(ReN)(n-) (n = 3, 4, 5) and [PW11O39(OsN)](2-). The rhenium- and osmium-nitrido effectively modify the electronic properties. The LUMOs in fully oxidized [PW11O39(ReN)](3-) and [PW11O39(OsN)](2-) are mainly concentrated on the Re and Os centers. The high-valent transition metals Re and Os modify the components and energies of the LUMO. The LUMO energies Of [PW11O39(ReN)](3-) and [PW11O39(OsN)](2-) are lower than that of related Keggin [PW12O40](3-). In addition, Re centers will prefer to accept the electrons in the first and second reduced process of fully oxidized [PW11O39(ReN)](3-).