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. Attached Files Name Description MIMEType Size Downloads 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.org/0000-0001-8616-365X 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 1521-3765 Keyword(s) bioinorganic chemistry ferrocene macrocycles sensing structure elucidation zinc 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 Persistent URL http://hdl.handle.net/10536/DRO/DU:30038946 Document type: Journal Article Collections: Centre for Material and Fibre Innovation GTP Research Related Links Link Description Connect to published version (restricted access) Go to link with your DU access privileges     Unless expressly stated otherwise, the copyright for items in DRO is owned by the author, with all rights reserved. Versions Version Filter Type Mon, 24 Oct 2011, 07:52:56 EST Tue, 25 Oct 2011, 10:31:01 EST Tue, 25 Oct 2011, 10:32:02 EST Mon, 27 Feb 2012, 15:37:02 EST Mon, 16 Jun 2014, 18:58:22 EST Thu, 11 Dec 2014, 17:20:05 EST Filtered Full Citation counts:   Cited 16 times in TR Web of Science Cited 16 times in Scopus Search Google Scholar Access Statistics: 751 Abstract Views, 1 File Downloads  -  Detailed Statistics Created: Mon, 24 Oct 2011, 07:52:56 EST