Self-assembled molecular hybrids comprising lacunary polyoxometalates and multidentate imidazole ligands.

Self-assembly via coordination bonding facilitates the creation of diverse inorganic-organic molecular hybrids with distinct structures and properties. Recent advances in this field have been driven by the versatility of organic ligands and inorganic units. Lacunary polyoxometalates are a class of well-defined metal-oxide clusters with a customizable number of reactive sites and bond directions, which make them promising inorganic units for self-assembled molecular hybrids. Herein, we report a novel synthesis method for self-assembled molecular hybrids utilizing the reversible coordination of multidentate imidazole ligands to the vacant sites of lacunary polyoxometalates. We synthesized self-assembled molecular hybrids including monomer, dimers, and tetramer, demonstrating the potential of our method for constructing intricate hybrids with tailored properties and functionalities.

Molecular hybrids of trivacant lacunary polyoxomolybdate and multidentate organic ligands.

Functional molecular inorganic-organic hybrids of lacunary polyoxometalates and organic ligands attract much attention for advanced material applications. However, the inherent instability of lacunary polyoxomolybdates hinders the synthesis of hybrids and their utilization. Herein, we present a viable approach for the synthesis of molecular hybrids of trivacant lacunary Keggin-type polyoxomolybdates and multidentate organic ligands including carboxylates and phosphonates, which is based on the use of a lacunary structure stabilized by removable pyridyl ligands as a starting material.

A protecting group strategy to access stable lacunary polyoxomolybdates for introducing multinuclear metal clusters.

Although metal-containing polyoxomolybdates (molybdenum oxide clusters) exhibit outstanding catalytic properties, their precise synthetic method has not yet been developed. This is mainly because the very low stability of the multivacant lacunary polyoxomolybdates limited their use as synthetic precursors. Here, we present a "protecting group strategy" in polyoxometalate synthesis and successfully develop an efficient method for synthesising multinuclear metal-containing polyoxomolybdates using pyridine as a protecting group for unstable trivacant lacunary Keggin-type polyoxomolybdate [PMo9O34]9-. Specifically, tetranuclear cubane- and planar-type manganese clusters were selectively synthesised in the polyoxomolybdates using the present method. The importance of this work is that, in addition to being the first practical way of utilizing multivacant lacunary polyoxomolybdates as precursors, this new "protecting group strategy" will make it possible to produce polyoxometalates with unexplored structures and properties.