Skip to main content
SpringerLink
Log in

Triphenylsulfonium topophotochemistry

  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. G. S. Egerton, J. M. Gleadle and A. G. Roach, Studies on aminoanthraquinone compounds IV-Photochemistry of some simple derivatives in solution and on polymer films, J. Soc. Dyers Colour., 1966, 82, 369; G. Olovsson, J. R. Scheffer, J. Trotter and C.-H. Wu, Novel differences between the solid state and solution phase photochemistry of 1,2-cyclodecanedione, Tetrahedron Lett., 1997, 38, 6549; C.-H. Tung and Y.-M. Ying, Photochemistry of phenyl phe- nylacetates adsorbed on pentasil andfaujasite zeolites, J. Chem. Soc., Perkin Trans. 2, 1997, 1319; T. Weisheit, D. Escudero, H. Petzold, H. Görls, L. González and W. Weigand, Photochemical behavior of (diphosphine)(η2- tolane)Pt0 complexes. Part A: Experimental considerations in solution and in the solid state, Dalton Trans., 2010, 39, 9493; A. Papagni, P. Del Buttero, C. Bertarelli, L. Miozzo, M. Moret, M. T. Pryce and S. Rizzato, Novel fluorinated amino-stilbenes and their solid-state photodimerization, New J. Chem., 2010, 34, 2612; V. Ramamurthy and S. Gupta, Supramolecular photochemistry: from molecular crystals to water-soluble capsules, Chem. Soc. Rev., 2015, 44, 119; A. Bricen and A. M. Escalona, Exploiting the use of multi- valent interactions in the design of photoreactive supra- molecular assemblies. From solution to crystal engineer- ing, Photochemistry, 2016, 43, 286.

    Article  CAS  Google Scholar 

  2. J. F. Cameron, N. Chan, K. Moore and G. Pohlers, Comparison of acid-generating efficiencies in 248 and 193-nm photoresists, Proc. SPIE, 2001, 4345, 106.

    Article  CAS  Google Scholar 

  3. J. L. Dektar and N. P. Hacker, Photochemistry of triaryl- sulfonium salts, J. Am. Chem. Soc., 1990, 112, 6004.

    Article  CAS  Google Scholar 

  4. J. W. Knapczyk and W. E. McEwen, Photolysis of triaryl- sulfonium salts in alcohol, J. Org. Chem., 1970, 35, 2539; J. L. Dektar and N. P. Hacker, A new mechanism for photo- decomposition and acid formation from triphenylsulpho- nium salts, J. Chem. Soc., Chem. Commun., 1987, 1591.

    Article  CAS  Google Scholar 

  5. S. Tagawa, S. Nagahara, T. Iwamoto, M. Wakita, T. Kozawa, Y. Yamamoto, D. Werst and A. D. Trifunac, Radiation and photochemistry of onium salt acid generators in chemically amplified resists, Proc. SPIE, 2000, 3999, 204.

    Article  CAS  Google Scholar 

  6. For a study on the reactivity of the diphenylsulfinyl radical cation, see: Y. Matsui, H. Sugawara, S. Seki, T. Kozawa, S. Tagawa and T. Itani, Difference in reaction schemes in photolysis of triphenylsulfonium salts between 248 nm and dry/wet 193 nm resists, Appl. Phys. Express, 2008, 1, 036001.

  7. K. M. Welsh, J. L. Dektar, M. A. Garcia-Garibaya, N. P. Hacker and N. J. Turro, Photo-CIDNP and nanosecond laser flash photolysis studies on the photodecomposition of triarylsulfonium salts, J. Org. Chem., 1992, 57, 4179.

    Article  CAS  Google Scholar 

  8. N. P. Hacker, D. V. Leff and J. L. Dektar, Cationic photo- initiators: Solid state photochemistry of triphenylsulfonium salts, Mol. Cryst. Liq. Cryst., 1990, 183, 505.

    CAS  Google Scholar 

  9. N. P. Hacker, J. L. Dektar, D. V. Leff, S. A. Macdonald and K. M. Welsh, The importance of the cage versus escape reactivity in the photochemistry of onium salts, J. Photopolym. Sci. Technol., 1991, 4, 445.

    Article  CAS  Google Scholar 

  10. N. P. Hacker and K. M. Welsh, Fluorescence Spectroscopy and Photochemistry of Poly(4-oxystyrenes) with Triphenylsulfonium Salts, Insight into the Photoinitiation of Chemically Amplified Resists, Adv. Chem. Ser., 1993, 236, 557; N. P. Hacker and K. M. Welsh, Photochemistry of tri- phenylsulfonium salts in poly[4-[(tert-butoxycarbonyl)oxy] styrene]: evidence for a dual photoinitiation process, Macromolecules, 1991, 24, 2137.

    Article  CAS  Google Scholar 

  11. S. Tsuji, S. Seki, T. Kozawa and S. Tagawa, Reaction mecha- nisms of excimer resists studied by laser flash photolysis, J. Photopolym. Sci. Technol., 2000, 13, 729.

    Article  CAS  Google Scholar 

  12. V. V. Boldyrev, Topochemistry and topochemical reactions, React. Solids, 1990, 8, 231.

    Article  CAS  Google Scholar 

  13. E. Kapetanakis, A. M. Douvas, P. Argitis and P. Normand, Radiation sensors based on the generation of mobile protons in organic dielectrics, ACS Appl. Mater. Interfaces, 2013, 5, 5667; D. G. Georgiadou, L. C. Palilis, M. Vasilopoulou, G. Pistolis, D. Dimotikali and P. Argitis, Incorporating triphenyl sulfonium salts in polyfluorene PLEDs: an all-organic approach to improved charge injec- tion, J. Mater. Chem., 2011, 21, 9296.

    Article  CAS  Google Scholar 

  14. N. Park, K. Park, M. Jang and S. Lee, One-pot synthesis of symmetrical and unsymmetrical aryl sulfides by Pd-cata- lyzed couplings of aryl halides and thioacetates, J. Org. Chem., 2011, 76, 4371.

    Article  CAS  Google Scholar 

  15. M. D. Pelta, H. Barjat, G. A. Morris, A. L. Davis and S. Hammond, Pulse sequences for high-resolution diffusion-ordered spectroscopy (HR-DOSY), Magn. Reson. Chem., 1998, 36, 706.

    Article  CAS  Google Scholar 

  16. H. Kunkely and A. Vogler, Photolysis of the ion pair triphenylsulfonium thiophenolate, Inorg. Chim. Acta, 2004, 357, 1292.

    Article  CAS  Google Scholar 

  17. W. W. Simons, The Sadtler Handbook of Ultraviolet Spectra, Sadtler Research Laboratories, Philadelphia, 1979.

    Google Scholar 

  18. J. L. Dektar and N. P. Hacker, Photochemistry of diaryliodo- nium salts, J. Org. Chem., 1990, 55, 639.

    Article  CAS  Google Scholar 

  19. F. H. Dill, W. P. Hornberger, P. S. Hauge and J. M. Shaw, Characterization of positive photoresist, IEEE Trans. Electron Devices, 1975, 445.

    Google Scholar 

  20. C. R. Szmanda, R. L. Brainard, J. F. Mackevich, A. Awaji, T. Tanaka, Y. Yamada, J. Bohland, S. Tedesco, B. Dal’Zotto, W. Bruenger, M. Torkler, W. Fallmann, H. Loeschner, R. Kaesmaier, P. M. Nealy and A. R. Pawloski, Measuring acid generation efficiency in chemically amplified resists with all three beams, J. Vac. Sci. Technol., B, 1999, 17, 3356.

    Article  CAS  Google Scholar 

  21. The periphery of the disc was not irradiated which is why TPS conversion does not reach 100%.

Download references

Acknowledgments

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).

Author information

Authors and Affiliations

  1. Beckman Institute, California Institute of Technology, Pasadena, California, 91125, USA

    E. Despagnet-Ayoub, W. W. Kramer, A. Sattler, J. R. Winkler & H. B. Gray

  2. The Dow Chemical Company, Formulation Science, Core R&D, 400 Arcola Road, Collegeville, Pennsylvania, 19426, USA

    W. Sattler

  3. Dow Electronic Materials, 455 Forest Street, Marlborough, Massachusetts, 01752, USA

    P. J. LaBeaume, J. W. Thackeray, J. F. Cameron, T. Cardolaccia & A. A. Rachford

Authors
  1. E. Despagnet-Ayoub
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. W. W. Kramer
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. W. Sattler
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. Sattler
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. P. J. LaBeaume
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. J. W. Thackeray
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. J. F. Cameron
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. T. Cardolaccia
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. A. A. Rachford
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. J. R. Winkler
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. H. B. Gray
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to E. Despagnet-Ayoub.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Despagnet-Ayoub, E., Kramer, W.W., Sattler, W. et al. Triphenylsulfonium topophotochemistry. Photochem Photobiol Sci 17, 27–34 (2018). https://doi.org/10.1039/c7pp00324b

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/c7pp00324b

Search

Navigation