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Updated: Jun 28, 2025
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Influence of Donor-Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores
Agustina Cotic1,2, Frank W Heinemann3, Leonardo D Slep1,2
1Departamento de Química Inorgánica, Analítica y Química Física, Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Pabellón 2, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina.
Abstract:
In MLCT chromophores, internal conversion (IC) in the form of hole reconfiguration pathways (HR) is a major source of dissipation of the absorbed photon energy. Therefore, it is desirable to minimize their impact in energy conversion schemes by slowing them down. According to previous findings on {Ru(bpy)} chromophores, donor-acceptor interactions between the Ru ion and the ligand scaffold might allow to control HR/IC rates. Here, a series of [Ru(tpm)(bpy)(R-py)]2+ chromophores, where tpm is tris(1-pyrazolyl)methane, bpy is 2,2'-bipyridine and R-py is a 4-substituted pyridine, were prepared and fully characterized employing electrochemistry, spectroelectrochemistry, steady-state absorption/emission spectroscopy and electronic structure computations based on DFT/TD-DFT. Their excited-state decay was monitored using nanosecond and femtosecond transient absorption spectroscopy. HR/IC lifetimes as slow as 568 ps were obtained in DMSO at room temperature, twice as slow as in the reference species [Ru(tpm)(bpy)(NCS)]+.
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