Extended Mo₃^IV-Polyoxometalates: 1D-[Mo₆^IVMo₄^VIGe₂ZnO₃₁py₉ (H₂O)]^4– and 2D-[Mo₃^IVMo₉^VIZn₆P₇O₅₆py₈]⁺ (py = Pyridine)

Abstract

The first examples of extended Mo₃^IV-polyoxometalates (Mo₃^IV-POMs), 1D-H₂ [Ge₂Mo₆^IVMo₄^VIO₃₁Zn(H₂O)py₉]·2Hpy·HOCH₂CH₂ OH^•4H₂O(H₂[1]·2Hpy^•glycol·H₂O) and 2D-[P@Mo₃^IVMo₉^VIZn₆(PO₄)₆O₃₂py₈]Cl·2py·7H₂O ([2]·Cl^•2py·7H₂O), were prepared through the solvothermal partial oxidation of [Mo₃^IVO₂(O₂CCH₃)₆(H₂O)₃]ZnCl₄ in py/H₂O containing glycol (for 1) or H₃PO₄ (for 2). They were characterized by X-ray crystallography and elemental analyses. Their electronic structure and bonding were discussed on the basis of density functional theory (DFT) theoretical calculations. X-ray photoelectron spectroscopy, IR/UV-vis spectra, powder X-ray diffraction, thermal gravimetric analysis, and mass spectrometry were also performed and discussed for 2D-2.