A systematic study has been carried out on the 3d divalent metal formate 3D magnetic frameworks templated by protonated amines, and the achievements have revealed that metal formate frameworks are very malleable, and their structures depend on the size, shape, charge, and hydrogen bonding geometries of the templating cations. Six kinds of metal formate frameworks have been created. They are chiral frameworks with a (49 · 66) topology, perovskite ones with a (412 · 63) topology, bi-nodal frameworks of (412 · 63)(49 · 66)n (n = 1, 2, 3) topologies, and porous diamond frameworks with 66 topology. These materials display promising and abundant magnetic, dielectric, porous, and optical properties and the possible combination of them. Therefore, they are of great interest for the study of molecule-based materials. It has been demonstrated that formate, being the smallest and simplest carboxylate, cheap and with low toxicity, thus more biocompatible and environmentally friendly, and having been more or less ignored, will find an important role in the construction of molecule-based materials and provide new materials with interesting properties.
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