Electronic Properties Of Polyoxometalate Derivatives [(C2b9h11) M ' M5o18](N-) (M '=Ti-Iv, Mo-Vi, W-Vi; M=Mo-Vi, W-Vi): Protonation, Electronic Spectra, And Redox Properties

Density functional theory is used to study the electronic structures and properties of Lindqvist-type polyoxometalates-supported organometallic compounds [LM'M5O18](n-) (L=[C2B9H11](2-) (Cb), [C5H5](-) (Cp); M' = Ti-IV,Mo-VI, W-VI; M=Mo-VI, W-VI). [(Cb) M'M5O18](n-) are a series of novel compounds designed in this work, based on related experiment. The calculated results reveal that the Cb ligand is able to form a sigma, 2 pi triple bond with M', which is similar to the bond character in [(Cp)M'M5O18](n-). However, comparing with the protonation, electronic spectra and redox properties of [(Cp) M'M5O18](n-) and [M'M5O19](n-), [(Cb)M'M5O18](n-) species show the advantageous electronic properties owning to the superior electron donating ability of the Cb ligand. (C) 2015 Wiley Periodicals, Inc.