Title: Synthesis and Characterization of Reversible Chemosensory Polymers: Modulation of Sensitivity through the Attachment of Novel Imidazole Pendants
Authors: Satapathy, Rudrakanta
Padhy, Harihara
Wu, Yen-Hsing
Lin, Hong-Cheu
Department of Materials Science and Engineering
Keywords: computational analysis;donor-acceptor systems;fluorescence;molecular wire effect;sensors;transduction material
Issue Date: 1-Dec-2012
Abstract: Three novel electron donoracceptor conjugated polymers (P1P3) bearing various imidazole pendants have been synthesized. Their excellent photophysical and electrochemical properties make them suitable transduction materials for chemosensing applications. Indeed, polymers P1P3 have been found to show remarkable sensing capabilities towards H+ and Fe2+ in semi-aqueous solutions. Upon titration with H+, polymers P1 and P2 showed hypsochromic shifts of their absorptions and photoluminescence (PL) maxima with enhanced fluorescence intensities. However, P3 showed diminished absorption and fluorescence intensities under similar conditions due to static quenching. The anomalous behavior of P3 compared with P1 and P2 has been clarified in terms of electronic distributions through computational analysis. Furthermore, P3 (KSV=1.03x107) showed a superior sensing ability towards Fe2+ compared with P1 (KSV=2.01x106) and P2 (KSV=4.12x106) due to its improved molecular wire effect. Correspondingly, the fluorescence lifetime of P3 was greatly decreased (almost 11-fold) compared to those of polymers P1 (4.6-fold) and P2 (6.2-fold) in the presence of Fe2+. By means of a fluorescence on-off-on approach, chemosensing reversibilities in protonationdeprotonation and metallationdemetallation have been achieved by employing triethylamine (TEA) and the disodium salt of ethylenediaminetetraacetic acid (Na2-EDTA)/phenanthroline, respectively, as suitable counter ligands. 1H NMR titrations have revealed the unique behavior of P3 compared with P1 and P2. To the best of our knowledge, there have been no previous reports of Fe2+ sensors based on single imidazole receptors conjugated to a main-chain polymer showing such a diverse sensitivity pattern depending on their attached substituents.
URI: http://dx.doi.org/10.1002/chem.201201437
ISSN: 0947-6539
DOI: 10.1002/chem.201201437
Volume: 18
Issue: 50
Begin Page: 16061
End Page: 16072
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