Authors
Vincenzo Langellotti, André Korzun, Morgan J McKee, Massimo Melchiorre, Taegeun Jo, J Felipe Estrada-Ruiz, Gregor Schnakenburg, Stefano Crespi, Francesco Ruffo, Nikolay Kornienko, Alessandro Bismuto
Published in
Chemistry (Weinheim an der Bergstrasse, Germany). Pages e71385. Jul 12, 2026. Epub Jul 12, 2026.
Abstract
π-Extended conjugation offers the opportunity to unveil new frontiers in materials, coupling redox activity with tunable photophysical properties. Here, we report a new family of π-conjugated salen ligands bearing phenylene bridges and tunable substituents, together with their corresponding boron difluoride complexes. Owing to the extended π-delocalization, these new compounds show promising results in electrochemical CO2 reduction to CO, achieving a remarkable Faradaic efficiency for an organocatalyst (up to 56%). Electrochemical, spectroscopic, and computational analyses support a ligand-centered mechanism in which single-electron reduction activates the framework for CO2 binding at the imine nitrogen, forming an N-bound CO2H intermediate. Beyond electrocatalysis, coordination to boron rigidifies the π-framework, producing emissive boron-salphen complexes with large Stokes shifts (>7000 cm- 1). These complexes function as efficient photosensitizers for singlet-oxygen generation, enabling mild oxidative cleavage of alkenes under blue-light irradiation. This work demonstrates that π-extension transforms the traditional salphen framework into a redox-active engine for small-molecule activation, bypassing the need for transition metals in CO2 electroreduction while simultaneously unlocking good photosensitizing capabilities.
PMID:
42437437
Bibliographic data and abstract were imported from PubMed on 12 Jul 2026.
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