4.7 Article

Multifunctional Interpenetrated 3D Supramolecular Structure Based on 1D Coordination Polymers: Selective Adsorption, Magnetism, Optical Property, Theoretical Analysis, and Electrical Conductivity

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CRYSTAL GROWTH & DESIGN
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AMER CHEMICAL SOC
DOI: 10.1021/acs.cgd.3c00175

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In this study, a paddle-wheel-based multifunctional one-dimensional coordination polymer (CP) was synthesized and characterized. The CP shows a tetragonal crystal structure and forms one-dimensional coordination chains connected by paddle wheel units. These chains are interpenetrated to form a three-dimensional supramolecular structure with channels hosting DMF molecules. The desolvated framework selectively adsorbs CO2 and exhibits semiconducting behavior with increased conductivity upon desolvation.
A paddle-wheel-based multifunctional 1D coordination polymer (CP) {[Cu-2(4-Cl-Bz)(4)(4,4'-bipy)](DMF)(2)}n (where 4-Cl-BzH = 4-chlorobenzoic acid, 4,4'-bipy = 4,4'-bipyridine, and DMF = dimethylformamide), (complex 1) have been synthesized via the solvothermal method and characterized by single-crystal X-ray diffraction analysis along with other spectroscopic studies. Structural analysis shows that 1 crystallizes in the tetragonal P4/ncc space group and 1D coordination chains are formed by connecting [Cu-2(4-Cl-Bz)(4)] paddle wheel units using 4,4'-bipy moieties along the crystallographic c axis. These 1D coordination chains are assembled to each other through weak ir...ir interactions to form interpenetrated 3D supramolecular structure, forming channels along the [1 1 0] and [-1 1 0] direction hosting DMF molecules. Hirshfeld surface analysis and corresponding 2D fingerprint plots indicate that ir...ir interaction is the major interaction among the coordination chains. Thermal analysis shows that guest DMF molecules are released within the temperature range of 70-150 degrees C and powder X-ray diffraction (PXRD) analysis reveals the quenching of the void space after removal of the solvent molecules. The desolvated framework selectively adsorbs CO2 over N-2. The magneto-luminescent behavior of the framework has also been studied. This ir- induced 3D supramolecular complex shows semiconducting behavior and conductivity increases upon desolvation.

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