Abstract
Single-crystal e.s.r. spectra of u.v.-irradiated octakis(methylammonium) decamolybdate(VI) dihydrate, [NH3Me]8[Mo8O26(MoO4)2]·2H2O, show the formation of two distinct localized MoVO5(OH) sites, resulting from a hydrogen-bonding proton transfer from [NH3Me]+ to a bridging oxygen atom in the anion. Analysis of the e.s.r. parameters g, 95,97Mo hyperfine structure, and 1H superhyperfine structure indicates the direct participation of the H 1s orbital in the semi-occupied molecular orbital with a spin population of 0.96–0.97 in MO 4d orbitals. From the direction of the maximum principal value of the 1H superhyperfine tensor, which lies close to the MOV⋯ H+(O) direction, two paramagnetic sites in the anion are determined and discussed in terms of the probability of the charge-transfer complex formation. One site has an arrangement of a MoO4 group and two terminal oxygen atoms (cis-dioxo-group) about the central molybdenum atom and another is composed of one terminal and five bridging oxygen atoms. It is suggested that [Mo8O26(MoO4)2]8 – suffers from the simultaneous multi-electron (up to four-electron) reduction photochemically.
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