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Abstract:

Photoexcitation of [Ru(tpy)(bpy)(μ-CN)Ru(py) 4 Cl] 2+ ([RuRu] 2+ ) at 387 nm results in the population of two 3 MLCT excited states of different symmetry that coexist on the nanosecond scale. Common to both states is an excited electron in a tpy-based orbital. Their configuration differs in the position of the hole. In one excited state, 3 MLCTz, the hole sits in an orbital parallel to the intermetallic axis allowing for a strong metal-metal electronic interaction. As a result, 3 MLCTz is highly delocalized over both metal centers and shows an intense photoinduced intervalence charge transfer (PIIVCT) NIR signature. In the other excited state, 3 MLCTxy, the hole is localized in an orbital perpendicular to the intermetallic axis and hence, significant intermetallic coupling is absent. This state shows no PIIVCT in the NIR and its spectrum is very similar to the one observed for the monometallic [Ru(tpy)(bpy)(CN)] + reference. Both 3 MLCT excited states have nanosecond lifetimes. The intervening energy barrier for a hole reconfiguration between the two different 3 MLCT excited states offers the opportunity to exploit wave functions of different symmetry before either the interconversion between them or the decay to the ground state is operative. © 2019 American Chemical Society.

Registro:

Documento: Artículo
Título:Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species
Autor:Oviedo, P.S.; Pieslinger, G.E.; Baraldo, L.M.; Cadranel, A.; Guldi, D.M.
Filiación:Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Quĺmica Inorgánica, Analĺtica y Quĺmica Fĺsica, Ciudad Universitaria, Pabellón 2, Buenos Aires, C1428EHA, Argentina
CONICET - Universidad de Buenos Aires, Instituto de Quĺmica-Fĺsica de Materiales, Medio Ambiente y Energĺa (INQUIMAE), Ciudad Universitaria, Pabellón 2, Buenos Aires, C1428EHA, Argentina
Department of Chemistry and Pharmacy, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen - Nürnberg, Egerlandstrasse 3, Erlangen, 91058, Germany
Palabras clave:Charge transfer; Ground state; Infrared devices; Intermetallics; Photoexcitation; Wave functions; Electronic interactions; Excited electrons; Interconversions; Intervalence charge transfer; Metal centers; MLCT excited state; Photo-induced; Single molecular species; Excited states
Año:2019
Volumen:123
Número:6
Página de inicio:3285
Página de fin:3291
DOI: http://dx.doi.org/10.1021/acs.jpcc.8b09499
Título revista:Journal of Physical Chemistry C
Título revista abreviado:J. Phys. Chem. C
ISSN:19327447
Registro:http://digital.bl.fcen.uba.ar/collection/paper/document/paper_19327447_v123_n6_p3285_Oviedo

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Citas:

---------- APA ----------
Oviedo, P.S., Pieslinger, G.E., Baraldo, L.M., Cadranel, A. & Guldi, D.M. (2019) . Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species. Journal of Physical Chemistry C, 123(6), 3285-3291.
http://dx.doi.org/10.1021/acs.jpcc.8b09499
---------- CHICAGO ----------
Oviedo, P.S., Pieslinger, G.E., Baraldo, L.M., Cadranel, A., Guldi, D.M. "Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species" . Journal of Physical Chemistry C 123, no. 6 (2019) : 3285-3291.
http://dx.doi.org/10.1021/acs.jpcc.8b09499
---------- MLA ----------
Oviedo, P.S., Pieslinger, G.E., Baraldo, L.M., Cadranel, A., Guldi, D.M. "Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species" . Journal of Physical Chemistry C, vol. 123, no. 6, 2019, pp. 3285-3291.
http://dx.doi.org/10.1021/acs.jpcc.8b09499
---------- VANCOUVER ----------
Oviedo, P.S., Pieslinger, G.E., Baraldo, L.M., Cadranel, A., Guldi, D.M. Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species. J. Phys. Chem. C. 2019;123(6):3285-3291.
http://dx.doi.org/10.1021/acs.jpcc.8b09499