Dynamic porous coordination polymers built-up from flexible 4,4'-dithiodibenzoate and rigid N-based ligands
Jarrah, Najmeh (Institut Català de Nanociència i Nanotecnologia)
Troyano, Javier (Institut Català de Nanociència i Nanotecnologia)
Carné-Sánchez, Arnau (Institut Català de Nanociència i Nanotecnologia)
Imaz, Inhar (Institut Català de Nanociència i Nanotecnologia)
Tangestaninejad, Shahram (University of Isfahan. Department of Chemistry)
Moghadam, Majid (University of Isfahan. Department of Chemistry)
Maspoch Comamala, Daniel (Institut Català de Nanociència i Nanotecnologia)

Fecha:	2020
Resumen:	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').
Ayudas:	European Commission 615954 Ministerio de Economía y Competitividad RTI2018-095622-B-I00 Ministerio de Economía y Competitividad SEV-2017-0706 Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-238
Nota:	Altres ajuts: it was also funded by the CERCA Program/Generalitat de Catalunya.
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Lengua:	Anglès
Documento:	Article ; recerca ; Versió acceptada per publicar
Materia:	1D coordination polymer ; 2D coordination polymers ; Coordination Polymers ; Functional testing ; Microporous coordination polymers ; Porous coordination polymer ; Structural transformation ; Thermal transformations
Publicado en:	Dalton transactions, Vol. 49, issue 37 (Oct. 2020) , p. 13142-13151, ISSN 1477-9234

DOI: 10.1039/d0dt02411b

Postprint 11 p, 1.1 MB

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