Abstract
Two isolated polyoxovanadogermanates, [Cd(C2H8N2)2]2{[Cd(C2H8N2)]2[Ge8V12O40(OH)8](H2O)}·7H2O (1, V12Ge8) and {[Cd(C2H8N2)2][Cd(C2H8N2)(H2O)]}{[Cd(C2H8N2)2][Cd(C2H8N2)]2Ge8V12O40(OH)8(H2O)}2·4H2O (2, V24Ge16), have been hydro-/solvothermally synthesized and structurally characterized. All the V ions existed in compounds 1 and 2 are demonstrated in the valence of +4 by bond valence calculation (BVC). Notably, it is the first time to investigate the nonlinear optical (NLO) properties of vanadium-based heteropolyacids and obtain strong two photon responses. The results of open aperture Z-scan based on the two compounds manifest that they are the highest value among the reported polyoxovanadates and may be a decent potential NLO materials. At the same time, the electrochemical and electrocatalytic properties of compounds 1 were also measured in detail. More interestingly, the ratio of compounds 1 and 2 in solvent thermal synthesis can be regulated by adjusting the proportion of mixed solvents, which provides a fresh idea and method for the investigation of polyoxometalate chemistry.
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