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

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

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 S3-sapphyrin and S4-rubyrin decrease steadily relative to STPPH and S2TPP owing to a higher rate of intersystem crossing. Furthermore, the protonated derivatives of S3-sapphyrin and S4-rubyrin encapsulate fluoride ions into their cavities with binding constants of 807 and 48 M-1 respectively. However, the triplet lifetime for S3-sapphyrin is longer (58.80 μs) than for normal thiaporphyrins (STPPH, 37.45 μs; S2TPP, 20.96 μs), suggesting that it could be very well suited for photosensitizing triplet oxygen.

Anion binding, Excited state dynamics, Expanded porphyrins, Rubyrin, Sapphyrin, Singlet, Triplet
1088-4246
305-314
Srinivasan, A.
a7690813-6a48-46d1-b016-f469a80eb066
Ravi Kumar, M.
c85cd253-ca82-4b50-8fe9-65e2a041f60d
Pandian, R. P.
c8376908-9219-4465-866d-de4a9d7773e5
Mahajan, S.
b131f40a-479e-4432-b662-19d60d4069e9
Simi Pushpan, K.
6151b61b-4aea-4e6c-b861-c1a1bb69e0f4
Sridevi, B.
f7b27895-8f35-471d-a364-11edff7ae1c1
Jayaprakash Narayanan, S.
4381aea0-2f99-4b55-8c37-4573d2574f90
Chandrashekar, T. K.
fe8c87c3-5a17-42ea-b7d4-e42332bfc922
Srinivasan, A.
a7690813-6a48-46d1-b016-f469a80eb066
Ravi Kumar, M.
c85cd253-ca82-4b50-8fe9-65e2a041f60d
Pandian, R. P.
c8376908-9219-4465-866d-de4a9d7773e5
Mahajan, S.
b131f40a-479e-4432-b662-19d60d4069e9
Simi Pushpan, K.
6151b61b-4aea-4e6c-b861-c1a1bb69e0f4
Sridevi, B.
f7b27895-8f35-471d-a364-11edff7ae1c1
Jayaprakash Narayanan, S.
4381aea0-2f99-4b55-8c37-4573d2574f90
Chandrashekar, T. K.
fe8c87c3-5a17-42ea-b7d4-e42332bfc922

Srinivasan, A., Ravi Kumar, M., Pandian, R. P., Mahajan, S., Simi Pushpan, K., Sridevi, B., Jayaprakash Narayanan, S. and Chandrashekar, T. K. (1998) Ground and excited state dynamics of core-modified normal and expanded porphyrins. Journal of Porphyrins and Phthalocyanines, 2 (4-5), 305-314. (doi:10.1002/(SICI)1099-1409(199807/10)2:4/5<305::AID-JPP72>3.0.CO;2-R).

Record type: Article

Abstract

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 S3-sapphyrin and S4-rubyrin decrease steadily relative to STPPH and S2TPP owing to a higher rate of intersystem crossing. Furthermore, the protonated derivatives of S3-sapphyrin and S4-rubyrin encapsulate fluoride ions into their cavities with binding constants of 807 and 48 M-1 respectively. However, the triplet lifetime for S3-sapphyrin is longer (58.80 μs) than for normal thiaporphyrins (STPPH, 37.45 μs; S2TPP, 20.96 μs), suggesting that it could be very well suited for photosensitizing triplet oxygen.

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More information

Published date: July 1998
Keywords: Anion binding, Excited state dynamics, Expanded porphyrins, Rubyrin, Sapphyrin, Singlet, Triplet

Identifiers

Local EPrints ID: 415724
URI: http://eprints.soton.ac.uk/id/eprint/415724
ISSN: 1088-4246
PURE UUID: eeb0cc3c-a218-4a6c-a6d3-70fe33fd7596
ORCID for S. Mahajan: ORCID iD orcid.org/0000-0001-8923-6666

Catalogue record

Date deposited: 21 Nov 2017 17:30
Last modified: 10 Nov 2021 03:18

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Contributors

Author: A. Srinivasan
Author: M. Ravi Kumar
Author: R. P. Pandian
Author: S. Mahajan ORCID iD
Author: K. Simi Pushpan
Author: B. Sridevi
Author: S. Jayaprakash Narayanan
Author: T. K. Chandrashekar

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