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Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
A Heterometallic Three-Dimensional Metal-Organic Framework Bearing an Unprecedented One-Dimensional Branched-Chain
Jing Chen1, Meng-Yao Chao1, Yan Liu1
1College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
Abstract:
A heterometallic metal-organic framework (MOF) of [Cd6Ca4(BTB)6(HCOO)2(DEF)2(H2O)12]∙DEF∙xSol (1, H3BTB = benzene-1,3,5-tribenzoic acid; DEF = N,N'-diethylformamide; xSol. = undefined solvates within the pore) was prepared by solvothermal reaction of Cd(NO3)2·4H2O, CaO and H3BTB in a mixed solvent of DEF/H2O/HNO3. The compatibility of these two divalent cations from different blocks of the periodic table results in a solid-state structure consisting of an unusual combination of a discrete V-shaped heptanuclear cluster of [Cd2Ca]2Ca' and an infinite one-dimensional (1D) chain of [Cd2CaCa']n that are orthogonally linked via a corner-shared Ca2+ ion (denoted as Ca'), giving rise to an unprecedented branched-chain secondary building unit (SBU). These SBUs propagate via tridentate BTB to yield a three-dimensional (3D) structure featuring a corner-truncated P41 helix in MOF 1. This outcome highlights the unique topologies possible via the combination of carefully chosen s- and d-block metal ions with polydentate ligands.
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