Mo3IV⋯[O8Mo4]3 Lewis acid–base cluster pairs: highly efficient and stable Lewis catalysis fields frustrated in crystalline nanoclusters

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 MoIV-polyoxomolybdates, [M2@(Mo3IVpy3)4Mo18Ox]q− (M = Al, V, Mo). Each [H4V2@(Mo3IVpy3)4Mo18O84]12− (2a) nanocluster is surrounded by 12 [V3Mo12O42] to build a Lewis catalysis field (LCF) composed of Mo3IV⋯[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.