Tetramethoxybenzene is a Good Building Block for Molecular Wires: Insights from Photoinduced Electron Transfer

Heinz, Luisa G. and Yushchenko, Oleksandr and Neuburger, Markus and Vauthey, Eric and Wenger, Oliver S.. (2015) Tetramethoxybenzene is a Good Building Block for Molecular Wires: Insights from Photoinduced Electron Transfer. Journal of Physical Chemistry A, 119 (22). pp. 5676-5684.

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Official URL: http://edoc.unibas.ch/dok/A6390978

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Two donor bridge–acceptor molecules with terminal triarylamine and Ru(bpy)32+ (bpy = 2,2′-bipyridine) redox partners were synthesized and investigated by cyclic voltammetry, optical absorption, luminescence, and transient absorption spectroscopy. The two dyads differ only by the central bridging unit, which was tetramethoxybenzene (tmb) in one case and unsubstituted phenylene (ph) in the other case. Photoirradiation of the Ru(bpy)32+ complex of the two dyads triggers intramolecular electron transfer from the triarylamine to the 3MLCT-excited metal complex, and this process occurs with time constants of 1.5 and 6.8 ns for the tmb- and ph-bridged dyads, respectively. Thermal electron transfer in the reverse direction then leads to disappearance of the photoproduct with a time constant of 10 ns in both dyads. The faster rate of photoinduced charge transfer in the tmb-bridged dyad can be understood in the framework of a hole-tunneling model in which the electron-rich tmb bridge imposes a more shallow barrier than the less electron-rich ph spacer. Until now tmb-based molecular wires have received very little attention, and alkoxy substituents have been mostly used for improving the solubility of oligo-p-phenylene vinylene (OPV) and oligo-p-phenylene ethynylene (OPE) wires. Our study illustrates how four alkoxy-substituents on a phenylene backbone can have a significant influence on the charge-transfer properties of a molecular wire, and this is relevant in the greater context of a future molecular electronics technology.
Faculties and Departments:05 Faculty of Science
05 Faculty of Science > Departement Chemie
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Heinz, Luisa and Neuburger, Markus
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
Note:Publication type according to Uni Basel Research Database: Journal article -- The final publication is available at American Chemical Society, see DOI link
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Last Modified:11 Jun 2018 08:46
Deposited On:03 Jul 2015 08:53

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