Solid-state 95Mo NMR of mixed-valence polyoxomolybdates (V, VI) with localized or delocalized electrons

We report solid-state 95Mo NMR of Mo V , Mo V,VI and Mo VI species in mixed-valence polyoxomolybdates (V, VI) with localized or delocalized d 1 electrons. Parameters about chemical shift and quadrupole interactions of 95Mo in diamagnetic crystals of [ Me 3 NH ] 6 [ H 2 Mo 12 V O 28 ( OH ) 12 ( Mo VI O 3 ) 4 ] · 2 H 2 O ( 1 ) with localized electrons and [ NMe 4 ] 2 [ NH 4 ] 8 [ ( Mo 6 VI Mo V O 23 ) 2 ] · 8 H 2 O ( 2 ) with delocalized ones were obtained by simulation of magic-angle-spinning (MAS) 95Mo NMR spectra. The isotropic and anisotropic chemical shifts of sites of Mo V in 1 and Mo V, VI in 2, respectively, exhibited absolute values quite larger than those of other Mo VI sites, which is examined by quantum chemical calculations.