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Different Topologies of Hg(II)-Bispidine 1D Coordination Polymers: Dynamic Behavior in Solvent Adsorption and Exchange Processes
Authors:Dr. Martina Lippi  Andrea Murelli  Prof. Patrizia Rossi  Prof. Paola Paoli  Prof. Dr. Massimo Cametti
Affiliation:1. Department of Chemistry, Materials and Chemical Engineering “Giulio Natta” Politecnico di Milano, Via Luigi Mancinelli, 7, 20133 Milano, Italy;2. Department of Industrial Engineering, Università degli Studi di Firenze, Via S. Marta 3, 50136 Firenze, Italy
Abstract:One-dimensional (1D) coordination polymers (CPs) featuring three different topologies, comprising zig-zag, ribbon-like and poly-[n]-catenane structures, were obtained by reaction of Hg(II) ions with a novel bispidine ligand L3 , and structurally characterized by SC- and P-XRD methods. The CPs obtained in the form of microcrystalline powders were tested for their ability to undergo solvent adsorption and exchange by P-XRD and 1H NMR spectroscopy. The extent of their dynamic behavior was then correlated to their structural features, highlighting the role of interchain interactions established among their constituting linear arrays. Zig-zag CPs proved to be resilient to external chemical stimuli, while they differently respond to thermal treatments, depending on the solvent originally included within the CP. In the case of polycatenated structures, we observed transformations where the original topology was maintained upon guest exchange, but also cases where it changed to zig-zag, even under solid/vapor conditions (i. e., no complete dissolution of the CP). Given the presence of linear interconnected 1D channels, 3 ⋅ ClBz-polycatenanePwd is also able to trap volatile guests such as n-hexane when exposed to its vapors.
Keywords:adsorption  coordination polymers  poly[n]catenanes  solvent exchange  X-ray structures
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