Anti-Kasha Conformational Photoisomerization of a Heteroleptic Dithiolene Metal Complex Revealed by Ultrafast Spectroscopy

Gazzetto, Michela; Artizzu, Flavia; Attar, Salahuddin S.; Marchiò, Luciano; Pilia, Luca; Rohwer, Egmont J.; Feurer, Thomas; Deplano, Paola; Cannizzo, Andrea (2020). Anti-Kasha Conformational Photoisomerization of a Heteroleptic Dithiolene Metal Complex Revealed by Ultrafast Spectroscopy. Journal of physical chemistry. A, 124(51), pp. 10687-10693. American Chemical Society 10.1021/acs.jpca.0c07794

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We investigated the anti-Kasha photochemistry and anti-Kasha emission of d8-metal donor–acceptor dithiolene with femtosecond UV–vis transient absorption spectroscopy and molecular modeling. Experimentally, we found a lifetime of 1.4 ps for higher excited states, which is exceptionally long when compared to typical values for internal conversion (IC) (10 s of fs or less). Consequently, a substantial emission originates from the second excited state. Molecular modeling suggests this to be a consequence of the spatially separated molecular orbitals of the first and second excited states, which gives a charge transfer character to the IC. More surprisingly, we found that the inherent flexibility of the molecule allows the metal complex to access different configurations depending on the photoexcited state. We believe that this unique manifestation of anti-Kasha photoinduced conformational isomerization is facilitated by the exceptionally long lifetime of the second excited state.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Institute of Applied Physics > NCCR MUST
08 Faculty of Science > Institute of Applied Physics
08 Faculty of Science > Institute of Applied Physics > Lasers

UniBE Contributor:

Gazzetto, Michela; Rohwer, Egmont Johann; Feurer, Thomas and Cannizzo, Andrea

Subjects:

500 Science > 530 Physics
500 Science > 540 Chemistry

ISSN:

1089-5639

Publisher:

American Chemical Society

Language:

English

Submitter:

Andrea Cannizzo

Date Deposited:

03 Mar 2021 10:03

Last Modified:

05 Mar 2021 06:41

Publisher DOI:

10.1021/acs.jpca.0c07794

BORIS DOI:

10.48350/151351

URI:

https://boris.unibe.ch/id/eprint/151351

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