Elsevier

Polyhedron

Volume 6, Issue 3, 1987, Pages 519-524
Polyhedron

Charge-transfer absorption spectra of some tungsten(VI) and molybdenum(VI) polyoxoanions

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Abstract

The charge-transfer (CT) absorption spectra in the UV region (30,000–50,000 cm−1) of most W(VI) and Mo(VI) polyoxoanions, attributed to the oxygen-to-metal transitions, are interpreted on the basis of structural considerations through edge- and/or corner-sharings of some octahedral units. Polyoxoanions studied here are classified into two groups according to a common fragment constituting their structures; one group contains an ‘M5O18’ fragment [M = W(VI) and Mo(VI)] such as Weakley-type [Ce(IV)(W5O18)2]8− anion, [W10O32]4− and [M′W5O19]n− [M′ = V(V), Nb(V), W(VI)] polyanions and the other contains an A-α-‘XM9O34’ fragment (X = heteroatom) such as Keggin-type [α-XM12O40]n− and Dawson-type [α-P2M18O62]6− heteropolyanions. The first- and second-lowest energy CT (LECT) bands of the respective group are qualitatively discussed from the CT interactions among some fragments.

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