Photoredox Processes in the Aggregation and Gelation of Electron-responsive Supramolecular Polymers Based on Viologens

TL;DR

This paper investigates how light-induced electron transfer in viologen-based supramolecular polymers triggers their aggregation and gelation, revealing mechanisms through electrochemical and spectro-electrochemical analyses.

Contribution

It introduces a novel light-controlled method to induce aggregation and gelation in electron-responsive supramolecular polymers based on viologens.

Findings

Light irradiation causes electron transfer and radical formation.

Photo-induced dimerization leads to network reorganization.

Irradiation conditions control aggregation or gelation.

Abstract

Viologen-based ditopic bis-pyridinyl-triazole bidentate ligands self-assemble in the presence of palladium ions into supramolecular polymers whose structure is imposed by the directed formation of coordination bonds. Light-irradiation of these electron-responsive supramolecular materials triggers a photo-induced electron transfer yielding isolated {\pi}-radicals and dimers of radicals. The photoreduction events and the associated dimerization steps trigger a large-scale reorganization occurring within the supramolecular network yielding aggregates or gels depending on the irradiation conditions (power, duration). Detailed electrochemical, spectro-electrochemical and photochemical analyses were conducted to understand the mechanisms at stakes in these light-induced aggregation and gelation.