“…{Mo 2 O 4 } 2+ clusters with metal d electrons localised in single metal–metal bonds occupy a prominent position among the polyoxometallates, which continue to be a subject of great interest because of their potential applications ranging from catalysis to medicine 1. Their basic building blocks, dinuclear {Mo 2 O 4 } 2+ moieties (Scheme ) with a well‐defined geometry,2,3 can assemble in many different ways and lead to a variety of metal oxide cores, as illustrated by some recently prepared clusters, i.e., [(Mo 2 O 4 ) 4 (OMe) 6 (MeOH) 4 Cl 2 ],4 bimetallic alkoxides [M 2 (Mo 2 O 4 ) 2 (O i Pr) 14 ] (M = Ta, Nb),5 [(Mo 2 O 4 ) 6 (μ 2 ‐SO 3 ) 12 (μ 3 ‐SO 3 ) 4 ] 20– ,6 [Na 4 (H 2 O) 6 {(Mo 2 O 4 ) 10 (P 2 O 7 ) 10 (CH 3 COO) 8 (H 2 O) 4 }] 24– ,7 [(Mo 2 O 4 ) 3 (O 3 PCH 2 PO 3 ) 3 (MoO 4 )] 8– ,8 [Na(H 2 O) 2 {(Mo 2 O 4 ) 4 (O 3 PCH 2 PO 3 ) 4 (CO 3 ) 2 }] 11– ,9 and a series of nano‐sized, mixed‐valence Mo V /Mo VI acetate complexes 10. Theoretical calculations have been performed on some of these species in order to understand the bonding of such complex architectures 11.…”