Work

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

Year: 2024

Type: article

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 / I 0 ), 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.

Source: Macromolecular Rapid Communications

DOI: 10.1002/marc.202400677