Polyoxometalates (POMs) have attracted increasing attention due to their intriguing structural diversity and diverse applications in drugs, magnetism, and catalysis. Lacunary POMs as precursors can induce transition metal (TM) cations’ aggregation to form TM oxo-clusters under hydrothermal conditions, producing a class of TM-added POMs with interesting physicochemical properties. Up to now, hydrothermal synthesis has been successfully used in creating a large number of TM-added POMs with unique physicochemical properties. Since 2007, we have reported a large number of organic-inorganic hybrid Ni6-added POMs under the guidance of lacunary directed strategy, using the lacunary sites of trilacunary POMs fragments {XW9O34}m− (X=P/Si/Ge, m=9, 10) as structure-directing agents (SDAs) to induce the TM-oxo clusters aggregation to form novel TM-added POMs. 1. Triangular M6-added POMs and dimer based on {XW9O34} fragments A series of structures with 1,2,3-arrayed triangular TM-added POMs {M6XW9} (M=Ni/Co/Cu, X=P/Si/Ge) and dimer have been obtained under hydrothermal conditions with the guidance of lacunary directed strategy. Considering the performance of acentric oxoboron cluster in nonlinear optics (NLO) and the existence of abundant controllable addition sites on hexa-nuclear Ni/Co/Cu-oxo clusters, we proposed the design syntheses via directed assembly strategy to combine acentric oxoboron clusters with the classical {M6XW9} and dimer-{M6XW9} units, aiming to construct metal-oxygen clusters with abundant structural types and acentric characters. 2. Sandwich M12-added POM and its extended structures A series of structures sandwich TM-added POMs {Cu12(XW9)2} (X=Si/Ge) have been obtained under hydrothermal conditions with the guidance of lacunary directed strategy. The sandwich Cu-added POMs {Cu12(XW9)2} have many sites that can occur addition reactions with oxoboron clusters. And there are different connection modes to expand the sandwich structure. These TM-added POMs are potential structural building units to link with acentric oxoboron clusters in the absence of organic amines, not only realizing the preparation of Ni/Co/Cu-B-O clusters added tungsten-oxygen clusters, but also expanding the application of POMs in NLO.

Lacunary directed synthesis of transition-metal-added POMs

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