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Host-guest complexes of calix[4]tubes - prediction of ion selectivity by quantum chemical calculations VI

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Abstract

The selectivity of the bis(calix[4]arene)tetraethylene abbreviated as calix[4]tube for the endohedral complexation of alkali and alkaline earth metal ions, was predicted on the basis of structures and complex formation energies computed with three different quantum chemical methods: DFT LANL2DZp)/LANL2DZp), PM3/SPASS, and PM6. A comparison with published X-ray structures demonstrated that the most reliable results were achieved applying DFT calculations. The complexation of K+ and Ba2+ is most favorable, followed by the encapsulation of Rb+ and Sr2+, respectively. The flexibility of the tube, described by the torsion angles associated with the ethylene linkages between the calix[4]arene units and phenyl rings intersecting the plane of the four methylene carbon atoms, also makes an important contribution to its selectivity. In general, the cavity size is similar to [2.2.2] and [N2N2N2], the cryptands with the largest cavities previously studied in our group applying a similar protocol.

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Acknowledgments

The authors gratefully acknowledge the Regionales Rechenzentrum Erlangen (RRZE) for a generous allotment of computer time. We would like to thank Prof. Tim Clark for productive discussions and for hosting this work at the CCC.

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  1. Inorganic Chemistry, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Egerlandstr. 1, 91058, Erlangen, Germany

    Svetlana Begel, Ralph Puchta & Rudi van Eldik

  2. Computer Chemistry Center, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Nägelsbachstr. 25, 91052, Erlangen, Germany

    Ralph Puchta

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  1. Svetlana Begel
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  2. Ralph Puchta
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Correspondence to Ralph Puchta.

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This paper belongs to a Topical Collection on the occasion of Prof. Tim Clark’s 65th birthday

For part V see: [50]

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Begel, S., Puchta, R. & van Eldik, R. Host-guest complexes of calix[4]tubes - prediction of ion selectivity by quantum chemical calculations VI. J Mol Model 20, 2200 (2014). https://doi.org/10.1007/s00894-014-2200-1

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