Porous Metal Phosphonate Frameworks: Construction and Physical Properties

Conspectus Porous metal phosphonate frameworks (PMPFs) as a subclass of metal–organic frameworks (MOFs) have promising applications in the fields of gas adsorption and separation, ion exchange and storage, catalysis, sensing, etc. Compared to the typical carboxylate-based MOFs, PMPFs exhibit higher thermal and water stability due to the strong coordination ability of the phosphonate ligands. Despite their robust frameworks, PMPFs account for less than 0.51% of the porous MOFs reported so far. This is because metal phosphonates are highly susceptible to the formation of dense layered or pillared-layered structures, and they precipitate easily and are difficult to crystallize. There is a tendency to use phosphonate ligands containing multiple phosphonate groups and large organic spacers to prevent the formation of dense structures and generate open frameworks with permanent porosity. Thus, many PMPFs are composed of chains or clusters of inorganic metal phosphonates interconnected by organic spacers. Using this feature, a wide range of metal ions and organic components can be selected, and their physical properties can be modulated. However, limited by the small number of PMPFs, there are still relatively few studies on the physical properties of PMPFs, some of which merely remain in the description of the phenomena and lack in-depth elaboration of the structure–property relationship. In this Account, we review the strategies for constructing PMPFs and their physical properties, primarily based on our own research. The construction strategies are categorized according to the number ( n = 1–4) of phosphonate groups in the ligand. The physical properties include proton conduction, electrical conduction, magnetism, and photoluminescence properties. Proton conductivity of PMPFs can be enhanced by increasing the proton carrier concentration and mobility. The former can be achieved by adding acidic groups such as −POH and/or introducing acidic guests in the hydrophilic channels. The latter can be attained by introducing conjugate acid–base pairs or elevating the temperature. Semiconducting PMPFs, on the other hand, can be obtained by constructing highly conjugated networks of coordination bonds or introducing large conjugated organic linkers π–π stacked in the lattice. In the case of magnetic PMPFs, long-range magnetic ordering occurs at very low temperatures due to very weak magnetic exchange couplings propagated via O–P–O and/or O(P) units. However, lanthanide compounds may be interesting candidates for single-molecule magnets because of the strong single-ion magnetic anisotropy arising from the spin–orbit coupling and large magnetic moments of lanthanide ions. The luminescent properties of PMPFs depend on the metal ions and/or organic ligands. Emissive PMPFs containing lanthanides and/or uranyl ions are promising for sensing and photonic applications. We conclude with an outlook on the opportunities and challenges for the future development of this promising field.