Recent developments in the crystal engineering of diverse coordination modes (0–12) for Keggin-type polyoxometalates in hybrid inorganic–organic architectures

• Classification of POM-based inorganic–organic hybrids, including two-component systems Class I) and three-component systems (Class II).
• Coordination ability of POMs and how it is influenced by the experimental conditions.
• Organic ligand families including, pyridinedicarboxylic acids, N-oxides and Schiff bases.

At present, research into polyoxometalates (POMs) is a hot topic in many scientific fields, mainly because of their vast range of potential applications. Recently, the coordination ability of POMs has attracted the attention of the scientific community because it allows them to behave as unusual inorganic ligands. A direct consequence of this ability is the assembly of high-dimensional architectures, which have been reported during the past decade. Thus, the present review considers the latest achievements in the construction of inorganic–organic hybrid materials based on POMs, with a specific focus on their various coordination modes, particularly Keggin-type anions, which are widely available. First, this huge family of compounds is classified based on the number of components in the system. Second, recent research into organic N and O-donor ligands is described.

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