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Issue 39, 2017
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The role of dispersion type metal⋯π interaction in the enantiotropic phase transition of two polymorphs of tris-(thienyl)bismuthine

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Abstract

Two polymorphs of tris(thienyl)bismuthine Bi(2-C4H3S)3 (1) were isolated upon crystallization from n-hexane at different temperatures. The high temperature form 1-HT crystallized at 269 K in the trigonal space group R[3 with combining macron], whereas the low temperature form 1-LT crystallized at 245 K in the triclinic space group P[1 with combining macron]. An enantiotropic phase transition was observed at 250 K showing a transition energy of 1.4 kJ mol−1. Both polymorphs reveal the formation of centrosymmetric dimers that are based on London dispersion type bismuth⋯π heteroarene interactions. These primary building units show additional dispersion type interactions between neighbouring dimers and as a result 2D networks are formed. DFT calculations on the model systems BiX3⋯π thiophene (X = Cl, Me) verify the hypothesis of a soft and shallow binding potential of the London dispersion type bismuth⋯π heteroarene interaction, providing an explanation for the reversibility of the phase transition.

Graphical abstract: The role of dispersion type metal⋯π interaction in the enantiotropic phase transition of two polymorphs of tris-(thienyl)bismuthine

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Publication details

The article was received on 14 Jul 2017, accepted on 08 Sep 2017 and first published on 08 Sep 2017


Article type: Paper
DOI: 10.1039/C7DT02567J
Citation: Dalton Trans., 2017,46, 13492-13501
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    The role of dispersion type metal⋯π interaction in the enantiotropic phase transition of two polymorphs of tris-(thienyl)bismuthine

    A. M. Preda, W. B. Schneider, D. Schaarschmidt, H. Lang, L. Mertens, A. A. Auer and M. Mehring, Dalton Trans., 2017, 46, 13492
    DOI: 10.1039/C7DT02567J

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