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

Original Paper

DOI: 10.1007/s00894-014-2328-z

Cite this article as:
Bandaru, S., English, N.J. & MacElroy, J.M.D. J Mol Model (2014) 20: 2328. doi:10.1007/s00894-014-2328-z

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.

Figure

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.

Keywords

Metal Cryptates DFT, Binding energies cis–trans isomers 

Supplementary material

894_2014_2328_MOESM1_ESM.doc (1.3 mb)
ESM 1(DOC 1382 kb)

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  1. 1.The SFI Strategic Research Cluster in Solar Energy ConversionUniversity College DublinDublin 4Ireland
  2. 2.School of Chemical and Bioprocess EngineeringUniversity College DublinDublin 4Ireland
  3. 3.Centre for Synthesis and Chemical BiologyUniversity College DublinDublin 4Ireland

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