Metal–Organic Frameworks with Low‐Valent Metal Nodes

Abstract

Metal-organic frameworks (MOFs) are crystalline, 2-and 3-dimensional coordination polymers formed by bonding interactions between metals and multitopic organic ligands. These are typically formed using hard Lewis basic organic ligands with high oxidation state metal ions. The use of low-valent metals as structural elements in MOFs is far less common, despite the widespread use of such metals for catalysis, luminescence, and other applications. This Minireview focuses on recent advances in the field of low-valent MOFs and offers a perspective on the future development of these materials.

Structure–property–performance relationship of vanadium- and manganese-based metal–organic frameworks and their derivatives for energy storage and conversion applications

“…20 Various MOFs have been fabricated using divalent or trivalent 3p metal ions, 3d transition metals, and lanthanides, while there are still challenges in synthesizing MOFs from high-valent metal ions. 21,22 The synthesis of MOFs with covalent bonds between metal ions contributing as nodes and organic ligands as spokes combined to produce open framework congurations was conducted by Furukawa et al, 23 who discussed the developments in the construction of higher-order mesoscopic superstructures containing nanocrystals. 24 Two examples of transition metals are vanadium and manganese, belonging to the 3d subfamily and having an electron conguration of 3d 3 4s 2 and 3d 5 4s 2 , respectively.…”