Goldenberg, L.M. and Skabara, P.J. and Roberts, D.M. and Berridge, R. and Ortí, E. and Viruela, P.M. and Pou-Amerigo, R. (2000) Electrochemical molecular recognition of silver cation by electropolymerised thieno[3 ',4 ': 5,6][1,4]dithiino[2,3-b]quinoxaline: a joint experimental and theoretical study. Journal of Materials Chemistry, 10 (11). pp. 2458-2465. ISSN 0959-9428Full text not available in this repository. (Request a copy from the Strathclyde author)
The novel annelated monomer thieno[3',4':5,6][1,4]dithiino[2,3-b]quinoxaline 1 has been electropolymerised on a variety of electrodes, resulting in films which are electroactive in non-aqueous and aqueous solution. The polymer films exhibit a transformation in voltammetric response corresponding to a positive shift in redox potential in the presence of silver cation, the maximum shift being ca. 150 mV in acetonitrile and ca. 400 epsilon mV in aqueous LiClO4 solution. Mercury dication demonstrates a similar, but smaller (ca. 130 mV) shift in aqueous solution. Theoretical calculations clearly show the potential of poly(1) as a metal complexation agent. The Ag+ ion coordinates with 1 in two ways: (i) an apical conformation involving the two dithiine sulfurs and (ii) a lateral sigma -complex with a contribution from the quinoxaline nitrogens. The Hg2+ ion prefers to coordinate with the sulfur atoms. The calculations performed for the trimer illustrate that the metal ions can be coordinated simultaneously by two repeat units in the polymer chain.
|Keywords:||molecular recognition, electropolymerisation, quinoxaline derivative, Chemistry, Materials Chemistry, Chemistry(all)|
|Subjects:||Science > Chemistry|
|Department:||Faculty of Science > Pure and Applied Chemistry|
|Depositing user:||Mr Derek Boyle|
|Date Deposited:||19 Apr 2006|
|Last modified:||29 Apr 2016 07:18|