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Electron Transfer across o-Phenylene Wires

Malzkuhn, Sabine and Guo, Xingwei and Häussinger, Daniel and Wenger, Oliver S.. (2019) Electron Transfer across o-Phenylene Wires. Journal of Physical Chemistry A, 123 (1). pp. 96-102.

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Official URL: https://edoc.unibas.ch/73097/

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Abstract

Photoinduced electron transfer across rigid rod-like oligo-p-phenylenes has been thoroughly investigated in the past, but their o-connected counterparts are yet entirely unexplored in this regard. We report on three molecular dyads comprised of a triarylamine donor and a Ru(bpy)32+ (bpy =2,2′-bipyridine) acceptor connected covalently by 2 to 6 o-phenylene units. Pulsed excitation of the Ru(II) sensitizer at 532 nm leads to the rapid formation of oxidized triarylamine and reduced ruthenium complex via intramolecular electron transfer. The subsequent thermal reverse charge-shift reaction to reinstate the electronic ground-state occurs on a time scale of 120–220 ns in deaerated CH3CN at 25 °C. The conformational flexibility of the o-phenylene bridges causes multiexponential transient absorption kinetics for the photoinduced forward process, but the thermal reverse reaction produces single-exponential transient absorption decays. The key finding is that the flexible o-phenylene bridges permit rapid formation of photoproducts storing ca. 1.7 eV of energy with lifetimes on the order of hundreds of nanoseconds, similar to what is possible with rigid rod-like donor–acceptor compounds. Thus, the conformational flexibility of the o-phenylenes represents no disadvantage with regard to the photoproduct lifetimes, and this is relevant in the greater context of light-to-chemical energy conversion.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Malzkuhn, Sabine and Guo, Xingwei and Häussinger, Daniel
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:1089-5639
e-ISSN:1520-5215
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:10 Dec 2019 15:35
Deposited On:10 Dec 2019 15:35

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