Multistep photochemical charge separation in rod-like molecules based on aromatic insides and diimides
Journal Article
·
· Journal of the American Chemical Society
- Argonne National Lab., IL (United States)
A series of intramolecular triads with linear, rod-like structures has been developed that undergo very efficient two-step electron transfer following direct excitation of a chromophore possessing a charge transfer (CT) excited state. The CT state of 4-aminonaphthalene-1,8-imide (ANI), produced by direct excitation of the chromophore, has about 70% of a negative charge transferred from the amine to the imide. Attachment of aniline (AN) and p-methoxyaniline (MeOAn) donors to ANI by means of a piperazine bridge results in linear dyads. An-ANI and MeOAn-ANI, that undergo rapid electron transfer in about 10{sup -11} s to give a >99% yield of the ion pairs, An{sup +}-ANI{sup -} and MeOAn{sup +}-ANI{sup -}, in which the charges are separated by 7.7 A. Further attachment of a 1,8:4,5-naphthalene-dimide (NI) electron acceptor to the imide group of ANI using a 2,5-dimethyphenyl spacer results in triads An-ANI-NI and MeOAn-ANI-NI. Excitation of the CT state of ANI within these triads results in the same high yield charge separation step observed in the corresponding dyads followed by a subnanosecond charge shift reaction to yield the giant dipole states An{sup +}-ANI-NI{sup -} and MeOAn{sup +}-ANI-NI{sup -} in 72% and 92% yield, respectively, in toluene. The lifetime of MeOAn{sup +}-ANI-NI{sup -} is 310 ns. These triad molecules make explicit use of a CT excited state to initiate a multistep electron transfer process. 67 refs., 10 figs., 4 tabs.
- Research Organization:
- Argonne National Laboratory (ANL), Argonne, IL
- DOE Contract Number:
- W-31109-ENG-38
- OSTI ID:
- 380871
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 28 Vol. 118; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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