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Title: Effect of micellar phase on the state and dynamics of some excited state charge transfer complexes. [Pyrene--N,N-dimethylaniline]

Abstract

The effect of micellar phase of kinetic processes of electron transfer reactions of exciplexes formed by pyrene (P) and N,N-dimethylaniline (DMA) has been studied. Transitory species are produced by a 10-ns pulse of 347.1-nm light from a Q-switched ruby laser and detected by rapid spectrophotometric or conduction techniques. Singlet excited pyrene (P*) readily accepts an electron from DMA to form an ion pair (P/sup -/ and DMA/sup +/), and the fate of the ion pairs depends critically on the micellar environment. In the case of cationic micelles, DMA/sup +/ is quickly expelled from the micellar surface while P/sup -/ is retained, leading to a long anion lifetime (approximately 500 ..mu..s). On the other hand, an anionic micellar surface traps DMA/sup +/ ions and enhances the geminate ion recombination process with P/sup -/. Several pyrene derivatives such as pyrenebutyric acid, pyrenesulfonic acid, pyrenetetrasulfonic acid, pyrenedodecanoic acid, and pyrenecarboxalydehyde which are solubilized at different sites in micelles are also selected as e/sup -/ acceptors to investigate the effect of separation between P* and DMA on the forward and back e/sup -/ transfer processes. Similar studies were carried out with the molecule P-(CH/sub 2/)/sub 3/-DMA which forms intramolecular exciplexes. Here neither ion canmore » escape from the exciplex owing to the restraint of the propyl chain. The physical and chemical properties of excited states of this molecule-miscellar system are dramatically different from those of intermolecular complexes. Micellar systems suggest the constituent ions of exciplexes. This has implications for conversion of light energy into ionic fragments which can be subsequently utilized.« less

Authors:
; ;
Publication Date:
Research Org.:
Univ. of Notre Dame, IN
OSTI Identifier:
6786915
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 100:6
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMINES; EXCITATION; PYRENE; CHARGE EXCHANGE; COMPLEXES; ELECTRON TRANSFER; FLUORESCENCE; MICELLAR SYSTEMS; SPECTRA; AROMATICS; CONDENSED AROMATICS; ENERGY-LEVEL TRANSITIONS; HYDROCARBONS; LUMINESCENCE; ORGANIC COMPOUNDS; 400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)

Citation Formats

Katusin-Razem, B, Wong, M, and Thomas, J K. Effect of micellar phase on the state and dynamics of some excited state charge transfer complexes. [Pyrene--N,N-dimethylaniline]. United States: N. p., 1978. Web. doi:10.1021/ja00474a007.
Katusin-Razem, B, Wong, M, & Thomas, J K. Effect of micellar phase on the state and dynamics of some excited state charge transfer complexes. [Pyrene--N,N-dimethylaniline]. United States. https://doi.org/10.1021/ja00474a007
Katusin-Razem, B, Wong, M, and Thomas, J K. Wed . "Effect of micellar phase on the state and dynamics of some excited state charge transfer complexes. [Pyrene--N,N-dimethylaniline]". United States. https://doi.org/10.1021/ja00474a007.
@article{osti_6786915,
title = {Effect of micellar phase on the state and dynamics of some excited state charge transfer complexes. [Pyrene--N,N-dimethylaniline]},
author = {Katusin-Razem, B and Wong, M and Thomas, J K},
abstractNote = {The effect of micellar phase of kinetic processes of electron transfer reactions of exciplexes formed by pyrene (P) and N,N-dimethylaniline (DMA) has been studied. Transitory species are produced by a 10-ns pulse of 347.1-nm light from a Q-switched ruby laser and detected by rapid spectrophotometric or conduction techniques. Singlet excited pyrene (P*) readily accepts an electron from DMA to form an ion pair (P/sup -/ and DMA/sup +/), and the fate of the ion pairs depends critically on the micellar environment. In the case of cationic micelles, DMA/sup +/ is quickly expelled from the micellar surface while P/sup -/ is retained, leading to a long anion lifetime (approximately 500 ..mu..s). On the other hand, an anionic micellar surface traps DMA/sup +/ ions and enhances the geminate ion recombination process with P/sup -/. Several pyrene derivatives such as pyrenebutyric acid, pyrenesulfonic acid, pyrenetetrasulfonic acid, pyrenedodecanoic acid, and pyrenecarboxalydehyde which are solubilized at different sites in micelles are also selected as e/sup -/ acceptors to investigate the effect of separation between P* and DMA on the forward and back e/sup -/ transfer processes. Similar studies were carried out with the molecule P-(CH/sub 2/)/sub 3/-DMA which forms intramolecular exciplexes. Here neither ion can escape from the exciplex owing to the restraint of the propyl chain. The physical and chemical properties of excited states of this molecule-miscellar system are dramatically different from those of intermolecular complexes. Micellar systems suggest the constituent ions of exciplexes. This has implications for conversion of light energy into ionic fragments which can be subsequently utilized.},
doi = {10.1021/ja00474a007},
url = {https://www.osti.gov/biblio/6786915}, journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 100:6,
place = {United States},
year = {1978},
month = {3}
}