Synthesis, x-ray structure of ferrocene bearing Bis(Zn-cyclen) complexes and the selective electrochemical sensing of TpT

Zeng, Zhanghua, Torriero, Angel A. J., Belousoff, Matthew J., Bond, Alan M. and Spiccia, Leone 2009, Synthesis, x-ray structure of ferrocene bearing Bis(Zn-cyclen) complexes and the selective electrochemical sensing of TpT, Chemistry : a European journal, vol. 15, no. 41, pp. 10988-10996, doi: 10.1002/chem.200901639.

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Title Synthesis, x-ray structure of ferrocene bearing Bis(Zn-cyclen) complexes and the selective electrochemical sensing of TpT
Author(s) Zeng, Zhanghua
Torriero, Angel A. J.ORCID iD for Torriero, Angel A. J.
Belousoff, Matthew J.
Bond, Alan M.
Spiccia, Leone
Journal name Chemistry : a European journal
Volume number 15
Issue number 41
Start page 10988
End page 10996
Total pages 9
Publisher Wiley - V C H Verlag GmbH & Co. KGaA
Place of publication Weinheim, Germany
Publication date 2009-10-19
ISSN 0947-6539
Keyword(s) bioinorganic chemistry
structure elucidation
Summary The new ligand, [Fc(cyclen)2] (5) (Fc=ferrocene, cyclen=1,4,7,10-tetraazacyclododecane), and corresponding ZnII complex receptor, [Fc{Zn(cyclen)(CH3OH)}2](ClO4)4 (1), consisting of a ferrocene moiety bearing one ZnII-cyclen complex on each cyclopentadienyl ring, have been designed and prepared through a multi-step synthesis. Significant shifts in the 1H NMR signals of the ferrocenyl group, cf. ferrocene and a previously reported [Fc{Zn(cyclen)}]2+ derivative, indicated that the two ZnII-cyclen units in 1 significantly affect the electronic properties of the cyclopentadienyl rings. The X-ray crystal structure shows that the two positively charged ZnII-cyclen complexes are arranged in a trans like configuration, with respect to the ferrocene bridging unit, presumably to minimise electrostatic repulsion. Both 5 and 1 can be oxidized in 1:4 CH2Cl2/CH3CN and Tris-HCl aqueous buffer solution under conditions of cyclic voltammetry to give a well defined ferrocene-centred (Fc0/+) process. Importantly, 1 is a highly selective electrochemical sensor of thymidilyl(3′-5′)thymidine (TpT) relative to other nucleobases and nucleotides in Tris-HCl buffer solution (pH 7.4). The electrochemical selectivity, detected as a shift in reversible potential of the Fc0/+ component, is postulated to result from a change in the configuration of bis(ZnII-cyclen) units from a trans to a cis state. This is caused by the strong 1:1 binding of the two deprotonated thymine groups in TpT to different ZnII centres of receptor 1. UV-visible spectrophotometric titrations confirmed the 1:1 stoichiometry for the 1:TpT adduct and allowed the determination of the apparent formation constant of 0.89±0.10×106 M−1 at pH 7.4.
Language eng
DOI 10.1002/chem.200901639
Field of Research 030604 Electrochemistry
030102 Electroanalytical Chemistry
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1.1 Refereed article in a scholarly journal
Copyright notice ©2009, Wiley-VCH Verlag GmbH&Co. KGaA
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