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Theoretical studies of separation of cis–trans isomers using dinuclear (Cu2+- and Zn2+-based) cryptates

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Abstract

Theoretical investigations have been carried out using density functional theory, with the M06L functional and SMD solvent-modeling, to study the binding interactions of geometrical cis-trans isomers of fumarate (fum2−), maleate (male2−) and 1,2-cyclopropane dicarboxylate with Cu2+- and Zn2+-based dinuclear cryptates. It was found that cis-trans isomers of these groups of compounds bind strongly to metal cryptates, and the binding ability of the cryptates is controlled by the shape of the ‘incoming’ isomer (cis or trans); trans isomers bind more strongly than cis. Due to the size and shape of the cis and trans isomers, the cryptates can bind selectively and, to a large extent, ‘recognize’ the various cis-trans isomers, suggesting the tantalising possibility of isomeric separation/purification and recognition.

Density functional theory calculations have been used to study the binding interactions of geometrical cis-trans isomers of fumarate (fum2−), maleate (male2−) and 1,2-cyclopropane dicarboxilate with Cu2+- and Zn2+-based dinuclear cryptates; Cu-based cryptate bound complexes are shown here. Cis-trans isomers bind strongly, and this is controlled by the shape of the ‘incoming’ isomer (cis or trans); trans isomers bind more strongly than cis. Binding is selective with ‘recognition’ of various cis-trans isomers.

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Acknowledgments

This material is based upon works supported by Science Foundation Ireland (SFI) under Grant No. [07/SRC/B1160]. We thank SFI and the Irish Centre for High-End Computing for the provision of high-performance computing facilities.

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Authors and Affiliations

  1. The SFI Strategic Research Cluster in Solar Energy Conversion, University College Dublin, Belfield, Dublin 4, Ireland

    Sateesh Bandaru, Niall J. English & J. M. D. MacElroy

  2. School of Chemical and Bioprocess Engineering, University College Dublin, Belfield, Dublin 4, Ireland

    Sateesh Bandaru, Niall J. English & J. M. D. MacElroy

  3. Centre for Synthesis and Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland

    Niall J. English & J. M. D. MacElroy

Authors
  1. Sateesh Bandaru
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  2. Niall J. English
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  3. J. M. D. MacElroy
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Corresponding authors

Correspondence to Sateesh Bandaru or Niall J. English.

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Bandaru, S., English, N.J. & MacElroy, J.M.D. Theoretical studies of separation of cis–trans isomers using dinuclear (Cu2+- and Zn2+-based) cryptates. J Mol Model 20, 2328 (2014). https://doi.org/10.1007/s00894-014-2328-z

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  • DOI: https://doi.org/10.1007/s00894-014-2328-z

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