Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction : a multi-technique mechanistic study

Vitõrica-Yrezábal, Iñigo J. and Libri, Stefano and Loader, Jason R. and Mínguez Espallargas, Guillermo and Hippler, Michael and Fletcher, Ashleigh J. and Thompson, Stephen P. and Warren, John E. and Musumeci, Daniele and Ward, Michael D. and Brammer, Lee (2015) Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction : a multi-technique mechanistic study. Chemistry - A European Journal, 21 (24). pp. 8799-8811. ISSN 0947-6539 (https://doi.org/10.1002/chem.201500514)

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Abstract

Despite an absence of conventional porosity, the 1D coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)3] ( 1 ; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into AgO bonds to yield coordination polymers [Ag4(O2C(CF2)2CF3)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(O2C(CF2)2CF3)4(TMP)2] formed by loss of TMP ligands exclusively from singly-bridging sites. Four polymorphic forms of 1 ( 1-ALT , 1-AHT , 1-BLT and 1-BHT ; HT=high temperature, LT=low temperature) have been identified crystallographically. In situ powder X-ray diffraction (PXRD) studies of the 1-ROH 1 2 transformations indicate the role of the HT polymorphs in these reactions. The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers. Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH / 1-AHT show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process.

  • Item type:Article
    ID code:53721
    Dates:
    Date
    Event
    28 May 2015
    Published
    11 May 2015
    Published Online
    23 March 2015
    Accepted
    Notes:This is the accepted version of the following article: Vitõrica-Yrezábal, I. J., Libri, S., Loader, J. R., Mínguez Espallargas, G., Hippler, M., Fletcher, A. J., ... Brammer, L. (2015). Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study. Chemistry - A European Journal , 21(24), 8799-8811. which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/chem.201500514/abstract
    Subjects:Science > Chemistry
    Technology > Chemical engineering
    Department:Faculty of Engineering > Chemical and Process Engineering
    University of Strathclyde > University of Strathclyde
    Depositing user: Pure Administrator
    Date deposited:14 Jul 2015 08:29
    Last modified:17 Apr 2024 00:21
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/53721
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