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Reversible crystal-to-crystal phase transition of a 4,4′-bipyridine-linked dinuclear copper(II) complex

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Abstract

The crystal-to-crystal phase transition of the previously reported dinuclear C i-symmetric complex [{Cu(NO3)2(phen)}2(4,4′-bipy)] (1) (phen = 1,10-phenanthroline; 4,4′-bipy = 4,4′-bipyridine) [Seidel et al. (2011) Z Anorg 637:1545–1554, 10] was studied in detail by differential scanning calorimetry (DSC), powder X-ray diffraction and variable temperature determinations of the unit cell parameters on a single-crystal. A density functional theory (DFT) study was undertaken to elucidate effects of crystal packing on the molecular structure in the solid-state. The DFT study confirmed that the molecular structures of 1 found in the solid-state do not represent the minimum energy conformation of the free molecule, especially with respect to the twist of the 4,4′-bipy bridging ligand. The DSC analysis revealed that the phase transition is a fully reversible process, and suggests that the relationship between the dimorphic forms of 1 is enantiotropic.

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Acknowledgments

The authors would like to thank Ulrich Holle for performing the PXRD analysis. Professors Christian W. Lehmann and Klaus-Richard Pörschke are gratefully acknowledged for their support.

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Authors and Affiliations

  1. Lehrstuhl für Analytische Chemie, Ruhr-Universität Bochum, Universitätsstraße 150, 44780, Bochum, Germany

    Rüdiger W. Seidel

  2. Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim, Germany

    Richard Goddard & Jürgen Breidung

  3. Mettler-Toledo GmbH, Ockerweg 3, 35396, Giessen, Germany

    Peter Bamfaste & Dirk Neff

  4. Institut für Anorganische Chemie, Rheinisch-Westfälische Technische Hochschule Aachen, Landoltweg 1, 52074, Aachen, Germany

    Iris M. Oppel

Authors
  1. Rüdiger W. Seidel
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  2. Richard Goddard
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  3. Jürgen Breidung
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  4. Peter Bamfaste
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  6. Iris M. Oppel
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Corresponding author

Correspondence to Rüdiger W. Seidel.

Electronic supplementary material

Atomic coordinates of the theoretical structures M1–M3 in SYBYL Mol2 format.

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Supplementary material 2 (TXT 4 kb)

Supplementary material 3 (TXT 4 kb)

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Seidel, R.W., Goddard, R., Breidung, J. et al. Reversible crystal-to-crystal phase transition of a 4,4′-bipyridine-linked dinuclear copper(II) complex. Struct Chem 24, 181–189 (2013). https://doi.org/10.1007/s11224-012-0044-9

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  • DOI: https://doi.org/10.1007/s11224-012-0044-9

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