Polyoxometalate-based frameworks with a linker of paddlewheel diruthenium(ii, iii) complexes

Abstract

The assembly reactions of a pivalate-bridged paddlewheel diruthenium(II, III) complex, [Ru₂^II,III(piv)₄(THF)₂]BF₄ (piv = pivalate), with three types of polyoxometalate (POM) clusters, (TBA)₂[Mo₆O₁₉] (TBA = tetra-n-butylammonium cation; Lindqvist-type Mo₆ POM), (TBA)₃[H₃V₁₀O₂₈] (V₁₀-type POM), and (THA)₃[PMo₁₂O₄₀] (THA = tetra-n-hexylammonium cation; Keggin-type Mo₁₂ POM), led successfully to the formation of one-, two-, and three-dimensional (1-, 2-, and 3-D) frameworks composed of [–{Ru₂}–POM–] inorganic linkages in (TBA)[{Ru₂(piv)₄}{Mo₆O₁₉}]·CH₂Cl₂·C₂H₄Cl₂ (1), (TBA)[{Ru₂(piv)₄}₂{H₃V₁₀O₂₈}]·C₂H₄Cl₂·7H₂O (2), and (THA)[{Ru₂(piv)₄}₂{PMo₁₂O₄₀}]·2(C₂H₄Cl₂) (3), respectively, where 1 is a 1-D linear chain, 2 forms a layered 2-D sheet framework, and 3 constructs a cristobalite-type 3-D structure.