Tuning porphyrin-quinone electronic coupling by varying polyparaphenylene spacer redox properties.

Format:

Book

Thesis/Dissertation

Author/Creator:

Allen, Rebecca Marie.

Contributor:

Therien, Michael J., advisor.

University of Pennsylvania.

Language:

English

Subjects (All):

Chemistry, Organic.

0490.

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

Local Subjects:

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

0490.

Physical Description:

260 pages

Contained In:

Dissertation Abstracts International 60-07B.

System Details:

Mode of access: World Wide Web.

text file

Summary:

This thesis focuses on the design, synthesis, characterization, optical spectroscopy, photophysical properties, and electrochemistry of novel porphyrin-spacer quinone electron transfer complexes. The goal of this work is to delineate the role spacer electronics play in modulating electronic coupling, and hence electron transfer rates. The polyparaphenylene spacer redox properties are systematically varied using different degrees of fluorine substitution; these model compounds will be used to investigate the effects of these changes in the ET medium electronic structure upon donor and acceptor coupling. The distance dependence of the ET rates will also be determined. Palladium-catalyzed cross -coupling methodologies were used to synthesize: {5-[4'-(2 ″,5″-benzoquinonyl-1″-yl)-2 ',5'-difluorophenyl-1'-yl]-10,20-diphenylporphinato}zinc(II), 5-[4'-(2″,5″-benzoquinonyl-1 ″-yl)-2',5'-difluorophenyl-1 '-yl]-10,20-diphenylporphyrin, {5-[4″-(2 ‴,5‴-benzoquinonyl-1‴-yl)[1 ',1″]2',5' ,2″,5″-tetrafluorobiphenyl-4 '-yl]-10,20-diphenylporphinato)zinc(II), 5-[4″ -(2‴,5‴-benzoquinonyl-1 ‴-yl) [1',1″]2 ',5',2″,5″ -tetrafluorobiphenyl-4'-yl]-10,20-diphenylporphyrin, {5-[4‴-(2″″,5 ″″-benzoquinonyl-1″ ″-yl)[1',1″,4 ″,1‴]2',5 ',2″,5″,2‴ ,5‴-hexafluoroterphenyl-4'-yl]-10,20-diphenylporphinato)zinc(II), 5-[4‴-(2″″,5 ″″-benzoquinonyl-1″ ″-yl)[1',1″,4 ″,1‴]-2',5 ',2″,5″,2‴ ,5‴-hexafluoroterphenyl-4'-yl]-10,20-diphenylporphyrin, {5-[4'-(2″,5″-benzoquinonyl-1 ″-yl)-2',3',5 ',6'-tetrafluorophenyl-1' -yl]-10,20-phenylporphinato}zinc(II), 5-[4'-(2 ″,5″-benzoquinonyl-1″-yl)-2 ',3',5',6' -tetrafluorophenyl-1'-yl]-10,20-phenylporphyrin, {5-[4″-(2‴,5‴-benzoquinonyl-1 ‴-yl)[1',1″] 2 ',3',5',6' ,2″,3″,5″,6 ″-octafluorobiphenyl-4'-yl]-10,20-diphenylporphinato}zinc(II), 5-[4″-(2‴,5‴-benzoquinonyl-1 ‴-yl)[1',1″] 2 ',3',5',6' ,2″,3″,5″,6 ″-octafluorobiphenyl-4'-yl]-10,20-diphenylporphyrin, {5-[4‴-(2″″,5 ″″-benzoquinonyl-1″ ″-yl)[1',1″,4 ″,1‴]2',3 ',5',6',2″ ,3″,5″,6″,2 ‴,3‴,5‴,6 ‴-dodecafluoroterphenyl-4'-yl]-10,20-diphenylporphinato}zinc(II), and 5-[4‴-(2″″,5 ″″-benzoquinonyl-1″ ″-yl)[1',1″,4 ″,1‴]2',3 ',5',6',2″ ,3″,5″,6″,2 ‴,3‴,5‴,6 ‴-dodecafluoroterphenyl-4'-yl]-10,20-diphenylporphyrin. These interesting molecules provide effective systems in which to study how spacer electronic structure determines both the magnitude of electron transfer rate constants as a function of distance and whether such tunneling events occur via electron or hole mediation mechanisms.

Notes:

Thesis (Ph.D. in Chemistry) -- University of Pennsylvania, 1999.

Source: Dissertation Abstracts International, Volume: 60-07, Section: B, page: 3279.

Supervisor: Michael J. Therien.

Local Notes:

School code: 0175.

ISBN:

9780599389526

Access Restriction:

Restricted for use by site license.