Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species

Beitrag in einer Fachzeitschrift


Details zur Publikation

Autorinnen und Autoren: Oviedo PS, Pieslinger GE, Baraldo LM, Cadranel A, Guldi DM
Zeitschrift: Journal of Physical Chemistry C
Jahr der Veröffentlichung: 2019
Band: 123
Heftnummer: 6
Seitenbereich: 3285-3291
ISSN: 1932-7447


Abstract

Photoexcitation of [Ru(tpy)(bpy)(mu-CN)Ru-(py)(4)Cl](2+) ([RuRu](2+)) at 387 nm results in the population of two (MLCT)-M-3 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 [Ru(tpy)(bpy)(CN)](+) reference. Both (MLCT)-M-3 excited states have nanosecond lifetimes. The intervening energy barrier for a hole reconfiguration between the two different (MLCT)-M-3 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.


FAU-Autorinnen und Autoren / FAU-Herausgeberinnen und Herausgeber

Guldi, Dirk Michael Prof. Dr.
Lehrstuhl für Physikalische Chemie I


Einrichtungen weiterer Autorinnen und Autoren

Universidad de Buenos Aires (UBA) / University of Buenos Aires


Zitierweisen

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. https://dx.doi.org/10.1021/acs.jpcc.8b09499

MLA:
Oviedo, Paola S., et al. "Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species." Journal of Physical Chemistry C 123.6 (2019): 3285-3291.

BibTeX: 

Zuletzt aktualisiert 2019-06-03 um 15:08