Modulando las interacciones en complejos paddle wheel de Ru25+

Tesis inédita de la Universidad Complutense de Madrid, Facultad de Ciencias Químicas, leída el 08-03-2024This Ph.D thesis is dedicating to revealing how the metal-ligand interactions in metal-metal bonded paddlewheel compounds affect the molecular orbital diagram of these species, which many times might hace importantt implications im thier phisical properties. To achive this aim. mixed-valence diruthenium paddlewheel complexes were chosen as test-bed models, and multiple ways of altering Ru2Ligand interactions were explored...Esta tesis doctoral está dedicada a revelar cómo las interacciones metal-ligando en compuestos de tipo paddlewheel con enlace metal-metal afectan afectan el diagrama de orbitales moleculares de esas especies, lo cual puede tener importantes implicaciones en sus propiedades físicas. Para lograr este objetivo, se eligieron complejos paddlewheel de di-rutenio con valencia mixta como modelos de prueba, y se exploraron múltiples formas de alterar las interacciones Ru2-ligando...Fac. de Ciencias QuímicasTRUEunpu

New insights into progressive ligand replacement from [Ru2Cl(O2CCH3)4]: synthetic strategies and variation in redox potentials and paramagnetic shifts

The complete series of [Ru2Cl(Dp-FPhF)x(O2CCH3)4−x] (x = 1–4; Dp-FPhF− = N,N′-bis(4-fluorophenyl)formamidinate) compounds, has been prepared and characterized by a multi-technique approach, including single crystal X-ray diffraction. A careful study of the different methodologies has allowed us to prepare four compounds with good yields and without an inert atmosphere or further purification. Specifically, [Ru2Cl(Dp-FPhF)(O2CCH3)3] (1) was obtained using an ultrasound-assisted (USS) method, while [Ru2Cl(Dp-FPhF)4] (4) was prepared by microwave assisted solvothermal synthesis (MWS). The intermediate substitution products cis-[Ru2Cl(Dp-FPhF)2(O2CCH3)2] (2) and [Ru2Cl(Dp-FPhF)3(O2CCH3)] (3) have been prepared by conventional heating, controlling the molar ratio of the starting materials. ESI-MS and infrared spectroscopy were used to follow all the reactions and permitted a qualitative evaluation of the axial reactivity in this series. Magnetic and absorption measurements confirmed a high spin σ2π4δ2(π*δ*)3 electronic configuration in all cases. However, the effect of the gradual modification of the electronic density in the diruthenium core markedly affects other properties. The cyclic voltammograms of the compounds show a strong decrease in the one electron oxidation potential and an increase in the reduction potential in the series from 1 to 4. Furthermore, despite their paramagnetic nature, 1H- and 19F-NMR spectra were recorded, and a correlation between the paramagnetic shift of the signals and the substitution degree of the diruthenium species was observed. These results provide a comprehensive guide to synthesise and understand the effects of equatorial ligand substitution on the properties of Ru25+ compounds.This research was funded by the Comunidad de Madrid and European Social Fund (project B2017/BMD-3770-CM). A. I. acknowledges the financial support from the UCM predoctoral grant no. CT42/18-CT43/18. A. T. also acknowledges the Universidad Complutense for a Predoctoral Grant (CT63/19-CT64/19) and the Spanish Ministry of Science and Innovation for a Postgraduate Fellowship at Residencia de Estudiantes (2020–2021 and 2021-2022).Peer reviewe