Products Cited in Publications Worldwide Porous and Self-Doped Conjugated Polyelectrolytes Exhibiting Open-Shell Character and Dual Ion-Electron Conduction

Porous and Self-Doped Conjugated Polyelectrolytes Exhibiting Open-Shell Character and Dual Ion-Electron Conduction

Medrano, Oscar; Zhou, Qiong; Shakir, Batul; Narváez-Lozano, Guillermo A; Hickey, Edward; Bayro, Marvin J; Bloch, Eric D; Vázquez, Ricardo Javier

DOI:

Abstract

Here, we report the synthesis and characterization of two porous two-dimensional conjugated polyelectrolytes (2D CPEs) exhibiting persistent room-temperature open-shell character (radical/ polaron) alongside dual ionic and electronic conductivity in aqueous environments. The 2D CPEs incorporate the self-doping, hydrophilic subunit potassium 4,4’-(4H-cyclopenta[2,1-b:3,4-b’]dithiophene-4,4-diyl)bis(butane-1-sulfonate) (CPDTSO3K2) with archetypal porous linkers: triphenylamine (2D CPE-TPA) and triphenyltriazine (2D CPE-TRZ). Gas physisorption measurements revealed BET (Langmuir) surface areas of 9.7 (10.4) m2·g−1 (N2) and 113 (341) m2·g−1 (CO2) for 2D CPE-TPA, and 23.7 (40.3) m2·g−1 (N2) and 142 (334) m2·g−1 (CO2) for 2D CPE-TRZ, comparable to archetypal porous polymers. Electron paramagnetic resonance (EPR) and UV−vis-NIR spectroscopy confirmed an open-shell configuration with Voigtian-shaped EPR signals. Solid-state EPR revealed a higher polaron concentration than in solution, specifically after acid-fumed exposure, revealing that intermolecular interactions enhance radical availability, stability, and interchain delocalization. Cyclic voltammetry indicated pseudocapacitive behavior with low turn-on potentials of 0.22 V (2D CPE-TPA) and 0.60 V (2D CPE-TRZ) vs Ag/AgCl. Electrochemical impedance spectroscopy estimated electrical conductivities of 1.1 mS·cm−1 (2D CPE-TPA) and 0.9 mS·cm−1 (2D CPE-TRZ), with Warburg analysis indicating higher ionic conductivity in 2D CPE-TPA (3.4 μS·cm−1) versus 2D CPE-TRZ (0.31 μS·cm−1), both correlating better with pore dimension rather than with overall porosity. Our findings underscore the role of self-doping moieties for persistent intermolecular radical formation and charge-ion transport, positioning 2D CPEs as promising electroactive porous and magnetic materials.

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