MoIV3⋯[O 8 Mo 4 ] 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 [Mo 3 O 2 (MeCO 2 ) 6 (H 2 O) 3 ] 2+ , more interstitial metal atoms were introduced to produce the largest nanoscale Mo IV -polyoxomolybdates, [M 2 @(MoIV3py 3 ) 4 Mo 18 O x ] q− (M = Al, V, Mo). Each [H 4 V 2 @(MoIV3py 3 ) 4 Mo 18 O 84 ] 12− ( 2a ) nanocluster is surrounded by 12 [V 3 Mo 12 O 42 ] to build a Lewis catalysis field (LCF) composed of MoIV3⋯[O 8 Mo 4 ] 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.