Uncovering Integrated Dual-State ESIPT-Conductivity, Redox-Capacity, and Opto-Electronic Responses Toward Hg(II)/ Cr(III) of Aliphatic Fluorescent Polymers.

Abstract

Excited-state intramolecular proton transfer (ESIPT)-associated dual-state emissive aliphatic dual-light emitting conducting polymers (DLECPs) having oxidation-reduction capacities are prepared polymerizing 2-acrylamido-2-methylpropane-1-sulfonic acid, methacrylic acid, and 2-methyl-3-(N-(2-methyl-1-sulfopropan-2-yl)acrylamido)propanoic acid monomers. Of as-synthesized DLECPs, nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopies, fluorescent enhancements (I/I₀), and computational investigation indicate intriguing photophysical features in DLECP3 (optimum composition). In DLECP3, ─CONH─, ─CON<, and ─COOH subluminophores are recognized by density-functional theory (DFT)/time-dependent-DFT calculations and experimental investigations. ESIPT-associated dual-state emission/conductivity, aggregation-enhanced emissions, selective opto-electronic responses toward Hg(II)/Cr(III) at 437/574 nm, and redox properties of DLECP3 are supported by solid-state/solution spectroscopies, time-correlated single photon counting (TCSPC) measurements, dual-state excitation dependent emissions, microscopic images, electrochemical measurements, and DFT calculations. Here, preferential interaction of Hg(II)/Cr(III) with DLECP3 (amide)/DLECP3 (imidol) and reduction/oxidation of Hg(II)/Cr(III) to Hg(I)/Cr(VI) are substantiated by UV-vis, FTIR, and X-ray photoelectron spectroscopies; TCSPC measurements; NMR-titration; electrochemical studies; alongside computational calculations. The proton-electrical conductivities of DLECP3, Hg(II/I)-DLECP3, and Cr(III/VI)-DLECP3 in solids/solutions are 15.27 × 10^-5/6.16 × 10^-5, 19.60 × 10^-5/25.52 × 10^-5, and 26.69 × 10^-5/27.60 × 10^-5 S cm^-1, respectively.