Frontiers in Chemistry (Jul 2018)
Controlling Thermal Expansion Behaviors of Fence-Like Metal-Organic Frameworks by Varying/Mixing Metal Ions
Abstract
Solvothermal reactions of 3-(4-pyridyl)-benzoic acid (Hpba) with a series of transition metal ions yielded isostructral metal-organic frameworks [M(pba)2]·2DMA (MCF-52; M = Ni2+, Co2+, Zn2+, Cd2+, or mixed Zn2+/Cd2+; DMA = N,N-dimethylacetamide) possessing two-dimensional fence-like coordination networks based on mononuclear 4-connected metal nodes and 2-connected organic ligands. Variable-temperature single-crystal X-ray diffraction studies of these materials revealed huge positive and negative thermal expansions with |α| > 150 × 10−6 K−1, in which the larger metal ions give the larger thermal expansion coefficients, because the increased space not only enhance the ligand vibrational motion and hinged-fence effect, but also allow larger changes of steric hindrance between the layers. In addition, the solid-solution crystal with mixed metal ions further validates the abundant thermal expansion mechanisms of these metal-organic layers.
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