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Published on: May 29, 2018
Ultrafast Dissipation via Interligand Electron Transfer in {Ru(tpy)(bpy)} Chromophores
Pedro O Abate1,2, Agustina Cotic1,2, Daiana Cabrosi1,2
1Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Química Inorgánica, Analítica y Química Física, Pabellón 2, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina.
None:
With the aim of studying interligand electron transfer (ILET) with different driving forces, [Ru(tpy)(R-bpy)(CN)]+ complexes with R-bpy = 4,4'-dimethylamino-2,2'-bipyridine (dMAb), 4,4'-dimethoxy-2,2'-bipyridine (dMeOb), 2,2'-bipyridine (bpy) or 4,4'-diethylester-2,2'-bipyridine (deeb) were synthesized and fully characterized using an arsenal of diffraction, electrochemical and spectroscopic techniques together with DFT/TD-DFT calculations. All the compounds studied here undergo ultrafast ILET in the picosecond or subpicosecond time scale, irrespective of the driving force or directionality of ILET, showing a typical Kasha behavior that dissipates energy before any potential bimolecular reactivity. This precludes the utilization of high-energy excited states, involving a non-LUMO excited electron, in solar-energy conversion strategies requiring diffusion-controlled reactivity.
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