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Probing metal cations with two new Schiff base bischromophoric pyrene based chemosensors: Synthesis, photophysics and interactions patterns

Catherine De Castro Orcid Logo, Tânia F.G.G. Cova, Alberto C.C. Pais, Daniela Pinheiro, Cristina Nuñez, Carlos Lodeiro, J. Sérgio Seixas de Melo

Dyes and Pigments, Volume: 134, Pages: 601 - 612

Swansea University Author: Catherine De Castro Orcid Logo

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Abstract

Two new pyrene chemosensors (bipyrenyl ligands L1 and L2) have been synthesized, fully characterized and their sensing ability towards metal cations (Cu2+, Ag+, Pb2+, Zn2+, Cd2+ and Hg2+) has been investigated by absorption and fluorescence (steady-state and time-resolved) techniques in solution. Th...

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Published in: Dyes and Pigments
ISSN: 0143-7208
Published: 2016
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URI: https://cronfa.swan.ac.uk/Record/cronfa40146
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Abstract: Two new pyrene chemosensors (bipyrenyl ligands L1 and L2) have been synthesized, fully characterized and their sensing ability towards metal cations (Cu2+, Ag+, Pb2+, Zn2+, Cd2+ and Hg2+) has been investigated by absorption and fluorescence (steady-state and time-resolved) techniques in solution. The absorption spectra of the two free ligands displays a single band (attributed to the monomer absorption) whereas the emission spectra show two bands, which were attributed to the emission of the monomer and dimer. For L1, time-resolved fluorescence measurements indicate the presence of a single component that becomes double exponential when the metal ion (in the investigated case, Pb2+) is added. From both steady-state and time-resolved data it is concluded that this dimer likely involves the interaction of two pyrene units, but the absence of a rising component in the fluorescence decays discards the possibility of the presence of a dynamic excimer. Upon addition of a metal ion, this band changes in shape mirroring the fact that a new complex, involving the metal ion and the ligand, is formed. From the overall spectroscopic and photophysical data rationalized by Hierarchical Cluster Analysis (HCA) and Principal Component Analysis (PCA) it was concluded that both L1 and L2 ligands are able to discriminate Ag+ and Pb2+ from all the other metal ions, with L2 displaying a higher sensing ability (as seen from HCA/PCA analysis) towards Pb2+. This global approach, joining spectral and photophysical data with multivariate analysis, has shown to constitute a powerful tool for revealing important patterns in this type of system.
Keywords: Pyrene, Chemosensors, Time-resolved fluorescence, Sensing ability, PCA, HCA
College: Faculty of Science and Engineering
Start Page: 601
End Page: 612