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Intramolecular Charge Transfer in Dimethylaminobenzonitrile and Related Aromatic Nitriles

Lee, Jae-kwang
http://rave.ohiolink.edu/etdc/view?acc_num=akron1258516378

Abstract Details

2009, Doctor of Philosophy, University of Akron, Chemistry.
The focus of this research is to investigate the mechanism of intramolecular charge transfer (ICT) in photoexcited 4-dimethylaminobenzonitrile (4-DMABN) and related aminobenzonitriles. Electronic absorption spectra of the low-lying ππ* and πσ* states of several dialkylaminobenzonitriles and 4-dimethylaminobenzethyne have been studied by time-resolved transient absorption and time-dependent density functional theory (TDDFT) calculation. In acetonitrile, the lifetime of the πσ*-state absorption is very short (picoseconds or subpicosecond) for molecules that exhibit intramolecular charge transfer, and very long (nanoseconds) for those that do not. Where direct comparison of the temporal characteristics of the πσ*-state and ICT-state transients could be made, the formation rate of the ICT state is identical to the decay rate of the πσ*-state within the experimental uncertainty. These results are consistent with the πσ*-mediated ICT mechanism, La (ππ*) πσ* ICT, in which the decay of the πσ*-state is determined by the rate of the solvent-controlled πσ* ICT charge-shift reaction. The ππ* πσ* state crossing does not occur in 3-dimethylaminobenzonitrile or 2-dimethylaminobenzonitrile, as predicted by the calculation, and 4-dimethylamino- benzethyne does not exhibit the ICT reaction, consistent with the higher energy of the ICT state relative to the πσ* state.
Edward C. Lim, PhD (Advisor)
162 p.
Chemistry
DMABN; DMABE; DIABN; TMABN; TICT; Intramolecular Charge Transfer Reaction; Time-resolved Transient Absorption; Femtosecond Laser Spectroscopy; TCSPC; &960; &963; *-mediated ICT mechanism

Recommended Citations

Citations

  • Lee, J.-K. (2009). Intramolecular Charge Transfer in Dimethylaminobenzonitrile and Related Aromatic Nitriles [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1258516378

    APA Style (7th edition)

  • Lee, Jae-kwang. Intramolecular Charge Transfer in Dimethylaminobenzonitrile and Related Aromatic Nitriles. 2009. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1258516378.

    MLA Style (8th edition)

  • Lee, Jae-kwang. "Intramolecular Charge Transfer in Dimethylaminobenzonitrile and Related Aromatic Nitriles." Doctoral dissertation, University of Akron, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=akron1258516378

    Chicago Manual of Style (17th edition)

akron1258516378
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© 2009, all rights reserved.
This open access ETD is published by University of Akron and OhioLINK.