One-flask synthesis of mono- and trifunctionalized 21-thia and 21-oxaporphyrin building blocks and their application in the synthesis of covalent and noncovalent unsymmetrical porphyrin arrays
DSpace at IIT Bombay
View Archive InfoField | Value | |
Title |
One-flask synthesis of mono- and trifunctionalized 21-thia and 21-oxaporphyrin building blocks and their application in the synthesis of covalent and noncovalent unsymmetrical porphyrin arrays
|
|
Creator |
GUPTA, I
RAVIKANTH, M |
|
Subject |
light-harvesting arrays
energy-transfer processes core-modified porphyrins excited-state dynamics electron-transfer multiporphyrin arrays coupling reactions conjugated groups appended systems rational design |
|
Description |
A rapid synthetic route has been developed to synthesize mono- and trifunctionalized 21-thia and 21-oxaporphyrin systems using simple precursors such as 2[alpha-(aryl)-alpha-hydroxymethyl] thiophene (thiophene mono-ol) and 2[alpha-(aryl)-alpha-hydroxymethyl] furan (furan mono-ol), respectively. Condensation of one equivalent of thiophene or furan mono-ol with two equivalents of aryl aldehyde and three equivalents of pyrrole under porphyrin forming conditions followed by column chromatography resulted in functionalized 21-thia or 21-oxaporphyrins. To synthesize monofunctionalized porphyrins, the mono-ol containing the functionalized aryl group was used. The functionalized aldehydes were used to synthesize trifunctionalized porphyrins. The mono-ol method is versatile and applicable to synthesize mono- and trifunctionalized 21-thia and 21-oxaporphyrins containing functional groups such as iodophenyl, ethynylphenyl, hydroxyphenyl, bromophenyl, and pyridyl groups. The monofunctionalized porphyrin building blocks containing iodophenyl and ethynylphenyl groups were used further to synthesize four unsymmetrical covalent porphyrin dimers containing two different porphyrin cores such as N3S-N-4, N3O-N4, and N3S-N3O bridged via diaryl ethyne group and one symmetrical phenylethyne bridged dimer containing two N3S cores. A preliminary photophysical study on these dimers indicated a possibility of energy transfer from one subunit to another. We also demonstrated the use of trifunctionalized porphyrins in the synthesis of two noncovalent unsymmetrical porphyrin tetramers containing one N3S and three N-4 porphyrin subunits.
|
|
Publisher |
AMER CHEMICAL SOC
|
|
Date |
2011-07-14T14:23:33Z
2011-12-26T12:48:26Z 2011-12-27T05:38:08Z 2011-07-14T14:23:33Z 2011-12-26T12:48:26Z 2011-12-27T05:38:08Z 2004 |
|
Type |
Article
|
|
Identifier |
JOURNAL OF ORGANIC CHEMISTRY, 69(20), 6796-6811
0022-3263 http://dx.doi.org/10.1021/jo040178u http://dspace.library.iitb.ac.in/xmlui/handle/10054/3981 http://hdl.handle.net/10054/3981 |
|
Language |
en
|
|