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Lanthanoid Complexation by a Tris-Tetrazole-Functionalised Calix[4]arene

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Authors
D'Alessio, D.
Skelton, B.
Sobolev, A.
Krause-Heuer, A.
Fraser, B.
Massi, Massimiliano
Ogden, Mark
Date
2016
Type
Journal Article

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D'Alessio, D. and Skelton, B. and Sobolev, A. and Krause-Heuer, A. and Fraser, B. and Massi, M. and Ogden, M. 2016. Lanthanoid Complexation by a Tris-Tetrazole-Functionalised Calix[4]arene. European Journal of Inorganic Chemistry. 2016 (34): pp. 5366-5372.
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European Journal of Inorganic Chemistry
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Department of Chemistry
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This is the peer reviewed version of the following article: D'Alessio, D. and Skelton, B. and Sobolev, A. and Krause-Heuer, A. and Fraser, B. and Massi, M. and Ogden, M. 2016. Lanthanoid Complexation by a Tris-Tetrazole-Functionalised Calix[4]arene. European Journal of Inorganic Chemistry. 2016 (34): pp. 5366-5372, which has been published in final form at http://doi.org/10.1002/ejic.201600938. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving at http://olabout.wiley.com/WileyCDA/Section/id-828039.html

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Abstract

The synthesis and characterization of 5,11,17,23-tetra-tert-butyl-25-hydroxy-26,27,28-tris(tetrazol-5-ylmethoxy)calix[4]arene is reported. Purification of the macrocycle required the use of preparative HPLC techniques. The macrocycle was found to be a poorer ligand for complexation of lanthanoid cations than the bis(tetrazole) analogue, but somewhat more effective than the tetrakis(tetrazole)-substituted derivative. Two metal complexes of the tris(tetrazole)-calixarene were structurally characterised. A polymeric sodium salt of the tris(tetrazole)-calixarene was isolated from a solution containing yttrium and a sodium acetate buffer. A praseodymium complex was isolated in the presence of an ammonium acetate buffer, where the calixarene acts as a unidentate ligand, bound to the metal atom through one tetrazole N-atom. Increasing the amount of buffer resulted in the crystallisation of a metal-free ammonium salt of the calixarene.