Dynamic porous coordination polymers built-up from flexible 4,4'-dithiodibenzoate and rigid N-based ligands
Herein we report the design, synthesis, structural characterisation and functional testing of a series of Cu(ii) coordination polymers containing flexible 4,4'-dithiodibenzoate ligand (4,4'-DTBA), with or without auxiliary N-donor ligands. Reaction of Cu(ii) with 4,4'-DTBA yielded a 1...
| Autores: | , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2020 |
| País: | España |
| Institución: | Universitat Autònoma de Barcelona |
| Repositorio: | Dipòsit Digital de Documents de la UAB |
| Idioma: | inglés |
| OAI Identifier: | oai:ddd.uab.cat:236000 |
| Acceso en línea: | https://ddd.uab.cat/record/236000 https://dx.doi.org/urn:doi:10.1039/d0dt02411b |
| Access Level: | acceso abierto |
| Palabra clave: | 1D coordination polymer 2D coordination polymers Coordination Polymers Functional testing Microporous coordination polymers Porous coordination polymer Structural transformation Thermal transformations |
| Sumario: | Herein we report the design, synthesis, structural characterisation and functional testing of a series of Cu(ii) coordination polymers containing flexible 4,4'-dithiodibenzoate ligand (4,4'-DTBA), with or without auxiliary N-donor ligands. Reaction of Cu(ii) with 4,4'-DTBA yielded a 1D coordination polymer (1) based on Cu(ii) paddlewheel units connected by 4,4'-DTBA, to form cyclic loop chains with intramolecular voids that exhibit reversible structural transformations upon subsequent solvent exchange in methanol to afford a new, crystalline, permanently-porous structure (1'). However, when the same reaction was run with pyridine, it formed a porous 2D coordination polymer (2). We have attributed the difference in dimensionality seen in the two products to the coordination of pyridine on the axial site of the Cu(ii) paddle-wheel, which forces flexible 4,4'-DTBA to adopt a different conformation. Reactions in the presence of 4,4'-bipyridine (4,4'-bpy) afforded two new, flexible, 2D coordination polymers (3 4). Lower concentrations of 4,4'-bpy afforded a structure (3) built from 1D chains analogous to those in 1 and connected through 4,4'-bpy linkers coordinated to the axial positions. Interestingly, 3 showed reversible structural transformations triggered by either solvent exchange or thermal treatment, each of which yielded a new crystalline and permanently porous phase (3'). Finally, use of higher concentrations of 4,4'-bpy led to a coordination polymer (4) based on a distorted CuO3N2 trigonal bipyramid, rather than on the Cu(ii) paddlewheel. The connection of these motifs by 4,4'-DTBA resulted in a zig-zag 1D chain connected through 4,4'-bpy ligands to form a porous 2D network. Interestingly, 4 also underwent reversible thermal transformation to yield a microporous coordination polymer (4'). |
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