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A general purpose reporter for cations: Absorption, fluorescence and electrochemical sensing of zinc(II)

Lookup NU author(s): Professor Andrew Benniston, Emeritus Professor Anthony Harriman, Donald Lawrie, Annabelle Mayeux, Dr Karen Rafferty

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Abstract

A fluorescent sensor has been synthesized that comprises a pyrene moiety tethered to a [2,2′:6′,2″]-terpyridyl ligand via a diethynylated thiophene linker. This multicomponent supermolecule is highly emissive in solution but addition of Zn2+ cations results in a drastic decrease in the fluorescence yield. Complexation between Zn2+ cations and the vacant terpyridyl ligand has been confirmed by NMR spectroscopy and by electrospray mass spectrometry. The ES-MS results provide strong support for the formation of both 1:1 and 1:2 (metal:ligand) complexes in solution. Complexation is further evidenced by a pronounced shift in the absorption spectrum, by the appearance of a long-wavelength band in the fluorescence spectrum and by cyclic voltammetry. On the basis of UV-visible spectrophotometric titrations, overall binding constants of logβ1 ≈ 5.1 and logβ2 ≈ 9.9 were derived for the 1:1 and 1:2 complexes, respectively, in acetonitrile solution. The possible application of this system as a generic chemical sensor for cationic species is mentioned.


Publication metadata

Author(s): Benniston AC, Harriman A, Lawrie DJ, Mayeux A, Rafferty K, Russell OD

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2003

Issue: 24

Pages: 4762-4769

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/b313413j

DOI: 10.1039/b313413j


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