title: Synthesis and characterization of reversible chemosensory polymers: modulation of sensitivity through the attachment of novel imidazole pendants.
abstract: Three novel electron donor-acceptor conjugated polymers (P1-P3) bearing various imidazole pendants have been synthesized. Their excellent photophysical and electrochemical properties make them suitable transduction materials for chemosensing applications. Indeed, polymers P1-P3 have been found to show remarkable sensing capabilities towards H(+) and Fe(2+) 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 (K(SV) = 1.03×10(7)) showed a superior sensing ability towards Fe(2+) compared with P1 (K(SV) = 2.01×10(6)) and P2 (K(SV) = 4.12×10(6)) 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 Fe(2+). By means of a fluorescence on-off-on approach, chemosensing reversibilities in protonation-deprotonation and metallation-demetallation have been achieved by employing triethylamine (TEA) and the disodium salt of ethylenediaminetetraacetic acid (Na(2)-EDTA)/phenanthroline, respectively, as suitable counter ligands. (1)H 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 Fe(2+) sensors based on single imidazole receptors conjugated to a main-chain polymer showing such a diverse sensitivity pattern depending on their attached substituents.
authors.affiliation: Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu, ROC Taiwan.
authors.forename: Rudrakanta
authors.initials: R
authors.lastname: Satapathy
authors.forename: Harihara
authors.initials: H
authors.lastname: Padhy
authors.forename: Yen-Hsing
authors.initials: YH
authors.lastname: Wu
authors.forename: Hong-Cheu
authors.initials: HC
authors.lastname: Lin
mesh_terms: D005456:Fluorescent Dyes / Q000737:chemistry*; D007093:Imidazoles / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D005456:Fluorescent Dyes; D007093:Imidazoles; D008024:Ligands; D011108:Polymers; C029899:imidazole; D007501:Iron