INQUIMAE 12526
INSTITUTO DE QUIMICA, FISICA DE LOS MATERIALES, MEDIOAMBIENTE Y ENERGIA
Unidad Ejecutora - UE
artículos
Título:
The Excited‐State Creutz‐Taube Ion
Autor/es:
PIESLINGER, GERMAN E.; CADRANEL, ALEJANDRO; RAMÍREZ-WIERZBICKI, IVANA
Revista:
Angewandte Chemie
Editorial:
WILEY-V C H VERLAG GMBH
Referencias:
Año: 2022 vol. 61
ISSN:
1433-7851
Resumen:
The excited-state version of the Creutz-Taube ion was prepared via visible light excitation of [(NH 3 ) 5 Ru II ( μ -pz)Ru II (NH 3 ) 5 ] 4+ . The resulting excited state is a mixed valence {Ru III?δ ( μ -pz ?? )Ru II+δ } transient species, which was characterized using femtosecond transient absorption spectroscopy with vis-NIR detection. Very intense photoinduced intervalence charge transfers were observed at 7500 cm -1 , revealing an excited-state electronic coupling element H DA = 3750 cm -1 . DFT calculations confirm a strongly delocalized excited state. A notable consequence of strong electron delocalization is the nanosecond excited state lifetime, which was exploited in a proof-of-concept intermolecular electron transfer. The excited-state Creutz-Taube ion is established as a reference, and demonstrates that electron delocalization in the excited state can be leveraged for artificial photosynthesis or other photocatalytic schemes based on electron transfer chemistry.
