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Ground and excited state dynamics of core-modified normal and expanded porphyrins

✍ Scribed by A. Srinivasan; M. Ravi Kumar; R. P. Pandian; S. Mahajan; K. Simi Pushpan; B. Sridevi; S. Jayaprakash Narayanan; T. K. Chandrashekar

Publisher: John Wiley and Sons
Year: 1998
Tongue: English
Weight: 265 KB
Volume: 02
Category: Article
ISSN: 1088-4246
DOI: 10.1002/(sici)1099-1409(199807/10)2:4/5<305::aid-jpp72>3.0.co;2-r

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✦ Synopsis

Singlet and triplet excited state data on two new core-modified expanded porphyrins and their protonated derivatives are reported. Absorption spectral studies indicate a gradual red shift of the absorption bands upon sulfur substitution into the core. The singlet lifetimes for expanded S~3~-sapphyrin and S~4~-rubyrin decrease steadily relative to STPPH and S~2~TPP owing to a higher rate of intersystem crossing. Furthermore, the protonated derivatives of S~3~-sapphyrin and S~4~-rubyrin encapsulate fluoride ions into their cavities with binding constants of 807 and 48 M^−1^respectively. However, the triplet lifetime for S~3~-sapphyrin is longer (58.80 μs) than for normal thiaporphyrins (STPPH, 37.45 μs; S~2~TPP , 20.96 μs), suggesting that it could be very well suited for photosensitizing triplet oxygen.

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