Synthesis and evaluation of thiosemicarbazones functionalized with furylmoieties as new chemosensors for anion recognition

A family of heterocyclic thiosemicarbazone dyes (3a-f and 4) containing furyl groups was synthesized in good yields, characterized and their response in acetonitrile in the presence of selected anions was studied. Acetonitrile solutions of 3a-f and 4 showed absorption bands in the 335-396 nm range which are modulated by the electron donor or acceptor strength of the heterocyclic systems appended to the thiosemicarbazone moiety. Fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulphate, nitrate, acetate and cyanide anions were used in recognition studies. From these anions, only sensing features were seen for fluoride, cyanide, acetate and dihydrogen phosphate. Two clearly different chromo-fluorogenic behaviours were observed: (i) a small shift of the absorption band due to the coordination of the anions with the thiourea protons and (ii) the appearance of a new red shifted band due to deprotonation. For the latter effect, a change in the colour of solution from pale yellow to purple was observed. Fluorescence studies were also in agreement with the different effects observed in the UV/Vis titrations. In this case, hydrogen bonding interactions were visible through the enhancement of the emission band, whereas deprotonation induced the appearance of a new red-shifted emission. Logarithms of stability constants for the two processes (complex formation + deprotonation) for receptors 3a-f in the presence of fluoride and acetate anions were determined from spectrophotometric titrations using the HypSpec V1.1.18 program. Semi-empirical calculations to evaluate the hydrogen-donating ability of the receptors and a prospective electrochemical characterization of compound 3b in the presence of fluoride were also performed. © 2012 The Royal Society of Chemistry.We thank the Spanish Government (project MAT2009-14564-C04-01) and the Generalitat Valenciana (project PROMETEO/2009/016) for support. We are also grateful to the Fundacao para a Ciencia e Tecnologia (Portugal) and FEDER-COMPETE for financial support through the Centro de Quimica - Universidade do Minho, Project PEst-C/QUI/UI0686/2011 (F-COMP-01-0124-FEDER-022716) and a Post-doctoral grant to R. M. F. Batista (SFRH/BPD/79333/2011). The NMR spectrometer Bruker Avance III 400 is part of the National NMR Network and was purchased within the framework of the National Program for Scientific Re-equipment, with funds from FCT. The authors are also indebted to the programme "Accoes Integradas Luso-Espanholas/CRUP", for bilateral agreement number E-144/10. Thanks also go to the Fundacion Carolina and UPNFM-Honduras for a doctoral grant to L. E. Santos-Figueroa and the Spanish Ministry of Science and Innovation for an FPU grant to M. E. Moragues.Santos Figueroa, LE.; Moragues Pons, ME.; Raposo, MMM.; Batista, RM.; Costa, SPG.; Ferreira, RCM.; Sancenón Galarza, F.... (2012). Synthesis and evaluation of thiosemicarbazones functionalized with furylmoieties as new chemosensors for anion recognition. Organic and Biomolecular Chemistry. 10(36):7418-7428. https://doi.org/10.1039/c2ob26200b741874281036Basabe-Desmonts, L., Reinhoudt, D. N., & Crego-Calama, M. (2007). Design of fluorescent materials for chemical sensing. Chemical Society Reviews, 36(6), 993. doi:10.1039/b609548hMartínez-Máñez, R., Sancenón, F., Hecht, M., Biyikal, M., & Rurack, K. (2010). Nanoscopic optical sensors based on functional supramolecular hybrid materials. 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