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RESEARCH ARTICLE

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Host–Guest Complexes of Bicyclic Hexaamine Cryptands – Prediction of Ion Selectivity by Quantum Chemical Calculations. III*

Ralph Puchta ^A ^B ^C , Roland Meier ^A and Rudi van Eldik ^A

+ Author Affiliations

- Author Affiliations

^A Institute for Inorganic Chemistry, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany.

^B Computer Chemistry Center, University of Erlangen-Nürnberg, Nägelsbachstrasse 25, 91052 Erlangen, Germany.

^C Corresponding author. Email: ralph.puchta@chemie.uni-erlangen.de

Australian Journal of Chemistry 60(12) 889-897 https://doi.org/10.1071/CH07238
Submitted: 14 July 2007 Accepted: 3 October 2007 Published: 4 December 2007

Abstract

Density functional theory (B3LYP/LANL2DZp) calculations on the structures and complex formation energies were performed to predict the alkali and alkaline earth ion selectivity of the cryptands 1,4,7,10,13,16,21,24-octaazabicyclo(8.8.8)hexacosane (N2N2N2) 1, 3,6,10,13,16,19-hexaazabicyclo(6.6.6)icosane (sarcophagine) 2 and 1,3,6,8,10,13,16,19-octaazabicyclo(6.6.6)icosane (sepulchrate) 3. Compounds 2 and 3 favour binding of Li⁺ and Mg²⁺ and exhibit a cavity size similar to [2.1.1], whereas cryptand 1 has a cavity size similar to [2.2.2] and prefers the selective binding of K⁺ and Ba²⁺. The cryptand flexibility of 1 is attributed mainly to the groups adjacent to the bridgehead nitrogens, whereas the main guiding feature for the flexibility of 2 and 3 can be traced back to the coordination of the ethylenediamine spacer.

Acknowledgements

The authors gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft as part of SFB 583. We thank Professor Tim Clark for hosting this work at the CCC, Nico van Eikema Hommes for helpful discussions, and the Regionales Rechenzentrum Erlangen (RRZE) for a generous allotment of computer time.

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^* For Prediction of Ion Selectivity by Quantum Chemical Calculations. II see: R. Puchta, R. van Eldik, Eur. J. Inorg. Chem. 2007, 1120. This article is dedicated to Professor Günther Grampp on the occasion of his 60th birthday.

^† [Li ⊂ 1]⁺: Nimag:1 (–87.6 cm^–1). [Be ⊂ 1]²⁺: Nimag:3 (–166.8, –134.3, –134.3 cm^–1).