title: Solvent-vapour-assisted pathways and the role of pre-organization in solid-state transformations of coordination polymers.
abstract: A family of one-dimensional coordination polymers, [Ag4(O2C(CF2)2CF3)4(phenazine)2(arene) n ]·m(arene), 1 (arene = toluene or xylene), have been synthesized and crystallographically characterized. Arene guest loss invokes structural transformations to yield a pair of polymorphic coordination polymers [Ag4(O2C(CF2)2CF3)4(phenazine)2], 2a and/or 2b , with one- and two-dimensional architectures, respectively. The role of pre-organization of the polymer chains of 1 in the selectivity for formation of either polymorph is explored, and the templating effect of toluene and p-xylene over o-xylene or m-xylene in the formation of arene-containing architecture 1 is also demonstrated. The formation of arene-free phase 2b , not accessible in a phase-pure form through other means, is shown to be the sole product of loss of toluene from 1-tol·tol [Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)]·2(toluene), a phase containing toluene coordinated to Ag(I) in an unusual μ:η(1),η(1) manner. Solvent-vapour-assisted conversion between the polymorphic coordination polymers and solvent-vapour influence on the conversion of coordination polymers 1 to 2a and 2b is also explored. The transformations have been examined and confirmed by X-ray diffraction, NMR spectroscopy and thermal analyses, including in situ diffraction studies of some transformations.
authors: Department of Chemistry, University of Sheffield , Brook Hill, Sheffield S3 7HF, UK.
authors: James S
authors: JS
authors: Wright
authors: Department of Chemistry, University of Sheffield , Brook Hill, Sheffield S3 7HF, UK.
authors: Iñigo J
authors: IJ
authors: Vitórica-Yrezábal
authors: Department of Chemistry, University of Sheffield , Brook Hill, Sheffield S3 7HF, UK.
authors: Harry
authors: H
authors: Adams
authors: Diamond Light Source, Harwell Science and Innovation Campus , Didcot, Oxfordshire OX11 0DE, UK.
authors: Stephen P
authors: SP
authors: Thompson
authors: European Synchrotron Radiation Facility , 6 rue J. Horowitz, 38042 Grenoble, France.
authors: Adrian H
authors: AH
authors: Hill
authors: Department of Chemistry, University of Sheffield , Brook Hill, Sheffield S3 7HF, UK.
authors: Lee
authors: L
authors: Brammer
keywords: coordination polymers; solid-state transformation; solvent-vapour-assisted conversion