Mo IV3⋯[O8Mo4]3 Lewis acid–base cluster pairs: highly efficient and stable Lewis catalysis fields frustrated in crystalline nanoclusters

Abstract

By using metal compounds or oxide/organic acid and enhanced reaction temperatures in the controlled solvothermal oxidation of [Mo₃O₂(MeCO₂)₆(H₂O)₃]²⁺, more interstitial metal atoms were introduced to produce the largest nanoscale Mo^IV-polyoxomolybdates, [M₂@(Mo^IV₃py₃)₄Mo₁₈O_x]^q− (M = Al, V, Mo). Each [H₄V₂@(Mo^IV₃py₃)₄Mo₁₈O₈₄]¹²⁻ (2a) nanocluster is surrounded by 12 [V₃Mo₁₂O₄₂] to build a Lewis catalysis field (LCF) composed of Mo^IV₃⋯[O₈Mo₄]₃ Lewis acid–base cluster pairs in the crystalline 2, accounting for the excellent and stable catalysis performance in the hydrazine reduction of nitroarenes to arylamines in varied solvents. The proposed new concept LCF provides a new way of thinking for designed synthesis and real applications of highly efficient LCF catalysts.