Electron Transfer around a Molecular Corner

Angewandte Chemie
Hauke C SchmidtOliver S Wenger

Abstract

The distance dependence of electron transfer (ET) is commonly investigated in linear rigid rod-like compounds, but studies of molecular wires with integrated corners imposing 90° angles are very rare. By using spirobifluorene as a key bridging element and by substituting it at different positions, two isomeric series of donor-bridge-acceptor compounds with either nearly linear or angled geometries were obtained. Photoinduced ET in both series is dominated by rapid through-bond hole hopping across oligofluorene bridges over distances of up to 70 Å. Despite considerable conformational flexibility, direct through-space and through-solvent ET is negligible even in the angled series. The independence of the ET rate constant on the total number of fluorene units in the angled series is attributed to a rate-limiting tunneling step through the spirobifluorene corner. This finding is relevant for multidimensional ET systems and grids in which individual molecular wires are interlinked at 90° angles.

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Citations

Aug 21, 2019·Chemistry : a European Journal·Vanessa C Arias-CoronadoSandra Bolaño
Nov 2, 2019·Chemistry : a European Journal·Alessandro CastrogiovanniOliver S Wenger
Apr 14, 2018·Journal of the American Chemical Society·Julia Nomrowski, Oliver S Wenger
Aug 14, 2020·The Journal of Physical Chemistry. a·Alexei CravcencoKarl Börjesson
Nov 22, 2019·The Journal of Physical Chemistry. a·Austin L Jones, Kirk S Schanze
Dec 29, 2018·The Journal of Physical Chemistry. a·Sabine MalzkuhnOliver S Wenger

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