Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study.
Despite an absence of conventional porosity, the 1D coordination polymer [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 ] (1; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into AgO bonds to yield coordination polymers [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 (ROH)2 ] (1-ROH; R=Me, Et, iPr). The reactions are reversible single-crystal-to-single-crystal transformations. Vapour-solid equilibria have been examined by gas-phase IR spectroscopy (K=5.68(9)×10(-5) (MeOH), 9.5(3)×10(-6) (EtOH), 6.14(5)×10(-5) (iPrOH) at 295 K, 1 bar). Thermal analyses (TGA, DSC) have enabled quantitative comparison of two-step reactions 1-ROH→1→2, in which 2 is the 2D coordination polymer [Ag4 (O2 …
Chemical transformations of a crystalline coordination polymer: a multi-stage solid–vapour reaction manifold
In its crystal structure the one-dimensional coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)3]n (1) (TMP = 2,3,5,6-tetramethylpyrazine) adopts a zig-zag arrangement in which pairs of silver(I) centres bridged by two fluorocarboxylate ligands are linked alternately via one or two neutral TMP ligands. This material can reversibly absorb/desorb small alcohols (ROH) in single-crystal-to-single-crystal transformations, despite the lack of porosity in the crystals, to yield a related material of formula [Ag4(O2C(CF2)2CF3)4(TMP)3(ROH)2]n (1-ROH). The absorption process includes coordination of the alcohol to silver(I) centres and, in the process, insertion of the alcohol into one-quarter of the Ag–O…
CCDC 1044598: Experimental Crystal Structure Determination
Related Article: Iñigo J. Vitórica-Yrezábal, Stefano Libri, Jason R. Loader, Guillermo Mínguez Espallargas, Michael Hippler, Ashleigh J. Fletcher, Stephen P. Thompson, John E. Warren, Daniele Musumeci, Michael D. Ward, Lee Brammer|2015|Chem.-Eur.J.|21|8799|doi:10.1002/chem.201500514
CCDC 1044595: Experimental Crystal Structure Determination
Related Article: Iñigo J. Vitórica-Yrezábal, Stefano Libri, Jason R. Loader, Guillermo Mínguez Espallargas, Michael Hippler, Ashleigh J. Fletcher, Stephen P. Thompson, John E. Warren, Daniele Musumeci, Michael D. Ward, Lee Brammer|2015|Chem.-Eur.J.|21|8799|doi:10.1002/chem.201500514
CCDC 1044597: Experimental Crystal Structure Determination
Related Article: Iñigo J. Vitórica-Yrezábal, Stefano Libri, Jason R. Loader, Guillermo Mínguez Espallargas, Michael Hippler, Ashleigh J. Fletcher, Stephen P. Thompson, John E. Warren, Daniele Musumeci, Michael D. Ward, Lee Brammer|2015|Chem.-Eur.J.|21|8799|doi:10.1002/chem.201500514
CCDC 1044596: Experimental Crystal Structure Determination
Related Article: Iñigo J. Vitórica-Yrezábal, Stefano Libri, Jason R. Loader, Guillermo Mínguez Espallargas, Michael Hippler, Ashleigh J. Fletcher, Stephen P. Thompson, John E. Warren, Daniele Musumeci, Michael D. Ward, Lee Brammer|2015|Chem.-Eur.J.|21|8799|doi:10.1002/chem.201500514