Role of the Bridge Length and Structure in Photoinduced Mixed-Valence Systems

Ramírez-Wierzbicki I, Slep LD, Cadranel A (2026)

Publication Type: Journal article

Publication year: 2026

Journal

Chemphotochem Wiley

Book Volume: 10

Article Number: e70254

Journal Issue: 9

DOI: 10.1002/cptc.70254

Abstract

The MLCT excited state of the Creutz–Taube analog [(NH3)5RuII(μ−4,4′-bpy)RuII(NH3)5]4+ was studied using femtosecond transient-absorption spectroscopy in combination with DFT/TD-DFT calculations. The computations show that strongly mixed dxz(Ru) orbitals, whose symmetry favors metal–metal interactions, are involved in the lowest-energy 3MLCT state. Detection of photoinduced IVCT transitions allowed to calculate, using comparative actinometry and the Mulliken–Hush formalism, an excited-state electronic coupling of HDA > 1510 cm–1. The influence of bridging-ligand conformation was analyzed in the context of ground-state versus excited-state mixed-valence interactions. Despite the long geometric donor–acceptor separation, hole delocalization promoted a two-order-of-magnitude extension of MLCT lifetimes relative to monometallic analogs.

Authors with CRIS profile

Alejandro Cadranel

Involved external institutions

Universidad de Buenos Aires (UBA) / University of Buenos Aires AR Argentina (AR)

How to cite

APA:

Ramírez-Wierzbicki, I., Slep, L.D., & Cadranel, A. (2026). Role of the Bridge Length and Structure in Photoinduced Mixed-Valence Systems. Chemphotochem, 10(9). https://doi.org/10.1002/cptc.70254

MLA:

Ramírez-Wierzbicki, Ivana, Leonardo D. Slep, and Alejandro Cadranel. "Role of the Bridge Length and Structure in Photoinduced Mixed-Valence Systems." Chemphotochem 10.9 (2026).

BibTeX: Download