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THE EXCITED STATE BEHAVIOR OF IMINIUM DERIVATIVES AND THEIR REDUCED FORMS.pdf (4.66 MB)
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The Excited State Behavior of Iminium Derivatives and Their Reduced Forms
Author Info
Zhou, Dapeng
Permalink:
http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1370525481
Abstract Details
Year and Degree
2013, Doctor of Philosophy (Ph.D.), Bowling Green State University, Photochemical Sciences.
Abstract
Photoinduced heterolytic bond cleavage is at the heart of many photochemical researches in renewable energy and biocatalysis. This dissertation outlines studies of photochemical heterolytic reactions involving the ‾OH and H‾ release from the iminium derivatives. In specific, the heterolytic properties of the iminium salt derivatives, such as N(5)-ethyl-4a-hydroxyflavin (Et-FlOH), 9-hydroxy-10-methyl-9-phenyl-9,10-dihydroacridine (AcrOH), and 10-methyl-9-phenyl-9,10-dihydroacridine (AcrH), were studied using transient absorption (TA) spectroscopy method. In the first part, the heterolytic property of Et-FlOH is studied, which is also related to understanding the photocatalytic mechanism of the bacterial bioluminescence. The heterolysis is not observed from the TA study of Et-FlOH except a fast S1→S0 decay. Combining with the results of time-dependent density functional theory calculations of Et-FlOH excited-states, a S1→S0 conical intersection (CI) is approved as the most important role for this fast decay. This identification proves that a rigid bio-condition is required to inhibit the formation of CI for this photocatalytic bacterial bioluminescence. In the second part, the excited state behavior of AcrOH is studied in different solvents via UV-vis TA spectroscopy. A fast heterolytic cleavage (τ = 108 ps) coupled with a ‾OH release is observed in the protic solvent, while intersystem crossing is observed in the aprotic solvent. This photoinduced heterolytic behavior exhibits the characteristic required for pOH jump catalytic research, such as the conformational changes in DNA/RNA and the release of drugs from host molecules. In the last part, a photoinduced hydride release from AcrH was investigated using TA spectroscopy. The hydride release is postulated to be a stepwise electron/H-atom transfer process from the triplet excited state of AcrH, and O
2
acts as an important electron acceptor in this process. These results show the high potential that, coupled with an inorganic catalyst, AcrH can be used as a photocatalyst in a bi-catalyst catalytic H
2
production system.
Committee
Ksenija Glusac (Advisor)
Alexander Tarnovsky (Committee Member)
R. Marshall Wilson (Committee Member)
Zhaohui Xu (Committee Member)
Pages
140 p.
Subject Headings
Chemistry
;
Optics
;
Physical Chemistry
Keywords
Photochemistry
;
Transient absorption spectroscopy
;
Photoinduced bond cleavage
;
Nonlinear optics
;
Excited state
;
AcrOH
;
AcrH
;
Et-FlOH
;
Laser
;
Hydroxyl release
;
Hydride release
;
Conical intersection
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Citations
Zhou, D. (2013).
The Excited State Behavior of Iminium Derivatives and Their Reduced Forms
[Doctoral dissertation, Bowling Green State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1370525481
APA Style (7th edition)
Zhou, Dapeng.
The Excited State Behavior of Iminium Derivatives and Their Reduced Forms.
2013. Bowling Green State University, Doctoral dissertation.
OhioLINK Electronic Theses and Dissertations Center
, http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1370525481.
MLA Style (8th edition)
Zhou, Dapeng. "The Excited State Behavior of Iminium Derivatives and Their Reduced Forms." Doctoral dissertation, Bowling Green State University, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1370525481
Chicago Manual of Style (17th edition)
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Document number:
bgsu1370525481
Download Count:
1,149
Copyright Info
© 2013, all rights reserved.
This open access ETD is published by Bowling Green State University and OhioLINK.