2000
DOI: 10.1021/ja991895m
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Solvent-Mediated Intramolecular Electron Transfer in U-Shaped Systems with Different “Bite Sizes”

Abstract: The rate of photoinduced charge separation is measured as a function of solvent for four donor (D)−bridge−acceptor (A) systems:  DMN[10]DCV, 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 … Show more

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Cited by 41 publications
(37 citation statements)
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References 36 publications
(64 reference statements)
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“…It is possible however that, in the absence of protein, the ribitol pathway is by-passed by shorter distance electron transfer tunnelling. This could be achieved either due to conformational flexibility of the ribotol allowing the isoalloxazine ring to approach the NB bridge 1 or it could be through intervening solvent molecules as observed for a variety of NB bridge molecules where through-bond tunnelling distances were considerable [73][74][75][76][77][78][79].…”
Section: Discussionmentioning
confidence: 99%
“…It is possible however that, in the absence of protein, the ribitol pathway is by-passed by shorter distance electron transfer tunnelling. This could be achieved either due to conformational flexibility of the ribotol allowing the isoalloxazine ring to approach the NB bridge 1 or it could be through intervening solvent molecules as observed for a variety of NB bridge molecules where through-bond tunnelling distances were considerable [73][74][75][76][77][78][79].…”
Section: Discussionmentioning
confidence: 99%
“…At the same time it was found that in this strongly bent system the rate is quite sensitive for the nature of the solvent employed. The latter we propose [25] to be caused by the fact that at 7.5 Å a single solvent molecule fits snugly in the cleft between D and A, thereby allowing through-solvent interaction to add to the overall electronic coupling between D and A.…”
Section: The Influence Of Bridge Bendingmentioning
confidence: 93%
“…While we have provided several examples supporting this prediction earlier [21][22][23][24], we have recently been able to demonstrate it in a really dramatic fashion and at the same time revealed an additional effect by comparing the rates of photoinduced charge separation in a series (see Figure 4) of three D-bridge-A systems in which the overall length of the bridge was kept constant but its configuration was changed from fully extended (D/A distance 13.4 Å) to partly bent (D/A distance 9.54 Å) and to strongly bent (D/A distance 7.5 Å) [25].…”
Section: The Influence Of Bridge Bendingmentioning
confidence: 98%
“…An alternative design based on superexchange mechanism 18 -20 of electronic coupling through a bridge ͑B͒ moiety in a donor-bridge-acceptor ͑DBA͒ complex has become a major motive in studies of long-range ET. [21][22][23][24][25][26][27][28][29][30][31][32] Although the superexchange coupling also decays exponentially with the DA separation, 6,26 the existence of a manifold of B states offers substantial flexibility for chemical design. A wide variety of bridging media including hydrocarbons, 27 proteins, 10,28,29,33,34 DNA, [35][36][37][38] and polyenes 39,40 has been considered for linear or bent DBA complexes.…”
Section: Introductionmentioning
confidence: 99%