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J.W. Solvent Mediated Intramolecular Electron Transfer In U-shaped Systems With Different `Bite-sizes.
Published 2000 · Chemistry
The rate of photoinduced charge separation is measured as a function of solvent for four donor (D)−bridge−acceptor (A) systems: DMNDCV, DMN[10nb]DCV, DMN[10cy]DCV, and DMAN[10cy]DCV. In the first three members of this series, the D/A pair is kept constant and contains the strong dimethoxynaphthalene (DMN) donor which enables detection of electron transfer over a wide range of solvent polarity. In the fourth member, DMN is substituted by a dimethoxyanthracene (DMAN) unit, which decreases the driving force for photoinduced charge separation by about 0.58 eV and thereby limits the occurrence of electron transfer to polar solvents. In all systems the bridge is held at a length of 10 σ bonds. The configuration of the bridge is, however, varied to increase its bending in the series, which leads to center-to-center D/A distances decreasing from 13.4 A in the first system to 9.54 A in the second, and 7.50 A in the latter two. In DMN[10nb]DCV, the rate of intramolecular charge separation over 9.54 A is always...