RT Journal Article
T1 Chemical tuning of the electronic structure in diruthenium compounds
A1 Lobato, Álvaro
A1 Inchausti Vallés, Almudena
A1 Mollfulleda, Rosa
A1 Swart, Marcel
A1 Perles, Josefina
A1 Herrero Domínguez, Santiago
A1 García Baonza, Valentín
A1 Taravillo Corralo, Mercedes
A1 Lobato Fernández, Álvaro
AB This study explores how the electronic structure of mixed valence diruthenium paddlewheel complexes can be controlled through chemical modifications. These compounds exhibit a unique electronic configuration due to the quasidegeneracy of π* and δ* orbitals, making them very attractive for applications in electronic, magnetic, catalytic, and bioinorganic systems. Through synthesis, electrochemical and spectroscopic analyses, and density functional theory (DFT) calculations, we have investigated the impact of axial ligand interactions, equatorial ligand electronic effects, and structural distortions on the molecular orbital diagram, paying special attention to how the δ*-π* gap is modified. In contrast to prior assumptions, our results show that variations in equatorial ligand donor strength shift orbital energies in parallel and, therefore, the observed UV/vis trends with Hammett-type substituents are primarily due to solvent-dependent conformational changes. Overall, our findings highlight the role of axial Ru–Cl interactions and torsion angle modifications in stabilizing spin-admixed or low-spin states, offering new pathways for controlling electronic configurations in bimetallic complexes.
PB American Chemical Society
YR 2023
FD 2023-09-16
LK https://hdl.handle.net/20.500.14352/129442
UL https://hdl.handle.net/20.500.14352/129442
LA eng
NO Inchausti, Almudena, et al. «Chemical Tuning of the Electronic Structure in Diruthenium Compounds». The Journal of Physical Chemistry Letters, vol. 16, n.o 38, septiembre de 2025, pp. 10000-08. DOI.org (Crossref), https://doi.org/10.1021/acs.jpclett.5c02176.
NO Universidad Complutense de Madrid
NO Universidad de Málaga
NO Agencia Estatal de Investigación (AEI)
DS Docta Complutense
RD 26 feb 2026