Building block approach to technetium-substituted polyoxotungstates

Abstract

Single-crystal X-ray structures of Na₁₄[Na₂(H₂O)₄Tc₂O₂(α-SiW₁₀O₃₇)₂]·35H₂O (Tc-POM-dimer) and Cs₇(Tc^VIO₄)trans-[Tc₂^IVPW₁₀O₃₉]·9H₂O (Tc-POM-chain) are the first X-ray structures for Tc-substituted polyoxometalates. Lacunary polyoxometalates accommodating Tc-dimers, impose asymmetry in crystal lattices without Tc/W disorder. Computation describes putative Tc^VIO₄²⁻ in Tc-POM-chain and explains Tc-connectivity in Tc-POM-dimer, which has characteristics of both POMs and metal-bonded dimers.