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Abstract
Receptors ferrocene–triazole–pyridine triads assembled with Zn(II) or Cd(II) metal cations behave as chemosensor molecules for HSO4 − anions through electrochemical and optical channels: the redox peak of the ferrocene/ferrocenium redox couple is shifted cathodically by 72–53 mV, and a new absorption band appeared in the UV–vis spectrum upon complexation with the HSO4 − anion. Association constants, detection limits and stoichiometries of the recognition processes have been determined, whereas 1H NMR experiments and density functional theory calculations are used to suggest the plausible binding mode taking place in the new supramolecular assembly formed.
Acknowledgements
We gratefully acknowledge the financial support MICINN-Spain (Project CTQ 2011/27175) and Fundación Séneca (Agencia de Ciencia y Tecnología de la Región de Murcia) project 04509/GERM/06 (Programa de Ayudas a Grupos de Excelencia de la Región de Murcia, Plan Regional de Ciencia y Tecnología 2007/2010).
Notes
1. OSWV technique has been employed to obtain well-resolved potential information, while the individual redox process is poorly resolved in the CV experiments in which individual E 1/2 potential cannot be easily or accurately extracted from the data.
2. Specfit/32 Global Analysis System, 1999–2004, Spectrum Software Associates ([email protected]). The Specfit program was acquired from Bio-logic, S.A. (Claix (Grenoble), France) (www.bio-logic.info) in January 2005.
3. In the inner part of the intermetallic axis, the hydrogenosulphate O–Zn bond (d
O–Zn = 2.114 Å; WBI = 0.199; LBO = 0.580; ) is stronger than the triflate O–Zn bond (d
O–Zn = 2.196 Å; WBI = 0.172; LBO = 0.488;
).
4. ORCA – an ab initio, DFT and semiempirical SCF-MO package. Written by Neese, F., Max Planck Institute for Bioinorganic Chemistry, D-45470 Mülheim/Ruhr, 2012. Version 2.9.0. Web page: http://www.mpibac.mpg.de/bac/logins/neese/description.php.
5. Loose convergence criteria for optimisations in ORCA: energy change 3.0 × 10− 5 hartree; maximum gradient 2.0 × 10− 3 hartree/a 0; RMS gradient 5.0 × 10− 4 hartree/a 0; maximum displacement 1.0 × 10− 2 a 0; RMS displacement 7.0 × 10− 3 a 0.