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As an important type of organic–inorganic hybrids, ionic and covalent polyoxometalate (POM) complexes with organic components have progressed rapidly over the past two decades. Due to the wide availability of organic building blocks and maneuverable combination styles, this field holds open opportunities now and in the near future. By abstracting the recent developments of POM complexes, some worthwhile topics are presented in this perspective. The important potentials of POM complexes are proposed to show in biological systems through ionic and covalent modification of biologically active molecules for immunosuppressive and therapeutic agents; in various functional materials with the incorporation of building and guest components for the construction of rigid/flexible nanostructures and frameworks; and in clean energy and environments via the combination of the photophysical and catalytic properties for chemical reactions with high efficiency.
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