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A three-dimensional NbO-type metal–organic framework (MOF) and its thin film on α-Al2O3 and SiO2 show novel reversible guest-dependent thermochromic behaviors.

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A ferroelectric MOF with a formula [Sr(μ-BDC)(DMF)]∞ (1) was transformed into [Sr(μ-BDC)(CH2Cl2)x]∞ (2) using a solvent exchange approach, where DMF = N,N-dimethylformamide and BDC(2-) = benzene-1,4-dicarboxylate. The lattice solvents, CH2Cl2 molecules, in 2 were removed by heating to give the solvent-free metal-organic framework [Sr(μ-BDC)]∞ (3) and the crystal-to-crystal transformation is reversible between 1 and 3. The release of DMF molecules from 1 results in the metal-organic framework of [Sr(μ-BDC)]∞ expanding a little along the a- and b-axes. The crystal structure optimizations for 1 and 3 disclosed that the lattice expansion is associated with the alternations of the bond distances and angles in the Sr(2+) ion coordination sphere along the a- and b-axes directions. The metal-organic framework 3 collapses at temperatures of more than 600 °C; such an extremely high thermal stability is related to the closed-shell electronic structure of the Sr(2+) ion, namely, the coordinate bond between the closed-shell Sr(2+) ion and the bridged BDC(2-) ligands does not have a preferred direction, which is favored for reducing lattice strains and is responsible for the higher thermal stability. The comparative investigations for the dielectric and ferroelectric behaviors of 1 and 3 confirmed that the motion of the polar DMF molecules, but not the [Sr(μ-BDC)]∞ framework, is responsible for the ferroelectric properties of 1.

A metal–organic-framework compound shows novel three-step dielectric relaxations arising from reorientational motion of polar guest molecules and its guest-free framework is a low-κ dielectric material.

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