Computational Study of Solvent Effects and the Vibrational Spectra of Anderson Polyoxometalates

The structures and vibrational frequencies of the type II Anderson heteropolyanions [TeMo 6 O 24 ] 6− and [IMo 6 O 24 ] 5− have been calculated by using density functional theory using a number of common functionals and basis sets. For the first time, Raman intensities have been calculated and the effect of solvent on the modeling has been investigated. The calculated IR and Raman spectral traces are in good agreement with experiment allowing the characteristic group frequencies for this class of polyoxometalate to be identified. The stretching vibrations of the molybdenum–oxygen bonds are predicted to occur at somewhat lower frequencies than in the type I polyoxometalates. Stretching of the heteroatom–oxygen bonds occurs at significantly lower frequencies than in the Keggin anions as a simple consequence of the higher coordination number of the central heteroatom in the Anderson systems. For the [Mo 2 O 7 ] 2− and [Mo 6 O 19 ] 2− ions, the relatively low negative charge leads to small structural changes when solvent is included. In these systems, solvent leads to an increase in the bond polarity and a decrease in the covalent bond orders, resulting in decreases in the calculated frequencies. For the Anderson anions, the higher negative charges leads to greater solvent effects with contraction of the clusters and increases in the frequencies of bands due to stretching of the two, cis ‐related molybdenum–oxygen bonds.