The hydrothermal syntheses of some inorganic–organic hybrids based on polyoxometallates, is surveyed. All compounds have been characterized using some physico–chemical approaches and single–crystal X–ray diffraction methods. Structural characterization by single–crystal X–ray diffraction reveals that these compounds consist of Keggin–type polyoxometallates, where a single {M3O13} triad is decorated with a trinuclear Ln complex. Moreover, the decorated polyanions are involved in a series of intermolecular interactions, such as hydrogen bonds and anion–π interactions, resulting in three–dimensional supramolecular architectures. Density functional theory (DFT) studies were conducted to support these intermolecular interactions in the hybrids, and have been rationalized using molecular electrostatic potential (MEP) surface calculations. We reported the first examples of hydrogen evolution reactivity (HER) of lanthanide- functionalized Keggin-based polyoxotungstates under photochemical and electrochemical conditions.

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