biostudies-literatureVitorica-Yrezabal IJScience and Technology Funding CouncilFunded AccessNuffield FoundationSpanish MINECOWhite Rose Consortium of Universities of Sheffield, Leeds and YorkMaterials Research Science and Engineering Center (MRSEC) programCambridge Crystallographic Data CentreEngineering and Physical Sciences Research CouncilNational Science Foundation8799-811https://www.ebi.ac.uk/biostudies/studies/S-EPMC4641464biostudies-literatureUnknown21(24)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 AgO 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 C(CF2 )2 CF3 )4 (TMP)2 ] formed by loss of TMP ligands exclusively from singly-bridging sites. Four pChemistry (Weinheim an der Bergstrasse, Germany)Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study.PMC4641464GR/T26047/01EP/F02195X/1DMR-1420073DMR-0820341Musumeci DHippler MVitorica-Yrezabal IJFletcher AJWard MDMinguez Espallargas GThompson SPWarren JEBrammer LLoader JRLibri SfalseCoordination 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 AgO 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 C(CF2 )2 CF3 )4 (TMP)2 ] formed by loss of TMP ligands exclusively from singly-bridging sites. Four p2015-01-01T00:00:00Z2015 Jun2025-04-19T23:29:23.957Z2019-03-27T02:01:43ZS-EPMC46414642596284410.1002/chem.201500514