A Caltech Library Service

Triphenylsulfonium topophotochemistry

Despagnet-Ayoub, E. and Kramer, W. W. and Sattler, W. and Sattler, A. and LaBeaume, P. J. and Thackeray, J. W. and Cameron, J. F. and Cardolaccia, T. and Rachford, A. A. and Winkler, J. R. and Gray, H. B. (2018) Triphenylsulfonium topophotochemistry. Photochemical and Photobiological Sciences, 17 (1). pp. 27-34. ISSN 1474-905X. doi:10.1039/c7pp00324b.

[img] PDF - Supplemental Material
See Usage Policy.


Use this Persistent URL to link to this item:


The products from the 193 nm irradiation of triphenylsulfonium nonaflate (TPS) embedded in a poly(methyl methacrylate) (PMMA) film have been characterized. The analysis of the photoproduct formation was performed using chromatographic techniques including HPLC, GPC and GC-MS as well as UV-vis and NMR spectroscopic methods. Two previously unreported TPS photoproducts, triphenylene and dibenzothiophene, were detected; additionally, GPC and DOSY-NMR spectroscopic analyses after irradiation suggested that TPS fragments had been incorporated into the polymer film. The irradiation of acetonitrile solutions containing 10% w/v PMMA and 1% w/v TPS in a 1 cm-path-length cuvette showed only a trace amount of triphenylene or dibenzothiophene, indicating that topochemical factors were important for the formation of these molecules. The accumulated evidence indicates that both products were formed by in-cage, secondary photochemical reactions: 2-(phenylthio)biphenyl to triphenylene, and diphenylsulfide to dibenzothiophene.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Despagnet-Ayoub, E.0000-0002-9013-7574
Sattler, W.0000-0001-5316-260X
Winkler, J. R.0000-0002-4453-9716
Gray, H. B.0000-0002-7937-7876
Additional Information:© 2017 The Royal Society of Chemistry and Owner Societies. The article was received on 25 Aug 2017, accepted on 03 Nov 2017 and first published on 03 Nov 2017. We thank Dr VanderVelde for his help on the DOSY-NMR experiment. This work was supported by the National Science Foundation Center for Chemical Innovation in Solar Fuels (CHE-1305124) and in part by The Dow Chemical Company through a university partnership program (Agreement # 227027AK). There are no conflicts to declare.
Group:CCI Solar Fuels
Funding AgencyGrant Number
Dow Chemical Company227027AK
Issue or Number:1
Record Number:CaltechAUTHORS:20171116-114003756
Persistent URL:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:83257
Deposited By: Tony Diaz
Deposited On:16 Nov 2017 21:16
Last Modified:15 Nov 2021 19:56

Repository Staff Only: item control page