Elucidating complex triplet-state dynamics in the model system isopropylthioxanthone
Summary: We introduce techniques for probing the dynamics of triplet states. We employ these tools, along with conventional techniques, to develop a detailed understanding of a complex chemical system: a negative-tone, radical photoresist for multiphoton absorption polymerization in which isopropylt...
| Main Authors: | , , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Elsevier
2022-01-01
|
| Series: | iScience |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2589004221015704 |
| _version_ | 1818975775335907328 |
|---|---|
| author | Nikolaos Liaros Sandra A. Gutierrez Razo Matthew D. Thum Hannah M. Ogden Andrea N. Zeppuhar Steven Wolf Tommaso Baldacchini Matthew J. Kelley John S. Petersen Daniel E. Falvey Amy S. Mullin John T. Fourkas |
| author_facet | Nikolaos Liaros Sandra A. Gutierrez Razo Matthew D. Thum Hannah M. Ogden Andrea N. Zeppuhar Steven Wolf Tommaso Baldacchini Matthew J. Kelley John S. Petersen Daniel E. Falvey Amy S. Mullin John T. Fourkas |
| author_sort | Nikolaos Liaros |
| collection | DOAJ |
| description | Summary: We introduce techniques for probing the dynamics of triplet states. We employ these tools, along with conventional techniques, to develop a detailed understanding of a complex chemical system: a negative-tone, radical photoresist for multiphoton absorption polymerization in which isopropylthioxanthone (ITX) is the photoinitiator. This work reveals that the same color of light used for the 2-photon excitation of ITX, leading to population of the triplet manifold through intersystem crossing, also depletes this triplet population via linear absorption followed by reverse intersystem crossing (RISC). Using spectroscopic tools and kinetic modeling, we identify the reactive triplet state and a non-reactive reservoir triplet state. We present compelling evidence that the deactivation channel involves RISC from an excited triplet state to a highly vibrationally excited level of the electronic ground state. The work described here offers the enticing possibility of understanding, and ultimately controlling, the photochemistry and photophysics of a broad range of triplet processes. |
| first_indexed | 2024-12-20T16:01:19Z |
| format | Article |
| id | doaj.art-d163417ba98545e7822f24570ad315d7 |
| institution | Directory Open Access Journal |
| issn | 2589-0042 |
| language | English |
| last_indexed | 2024-12-20T16:01:19Z |
| publishDate | 2022-01-01 |
| publisher | Elsevier |
| record_format | Article |
| series | iScience |
| spelling | doaj.art-d163417ba98545e7822f24570ad315d72022-12-21T19:34:17ZengElsevieriScience2589-00422022-01-01251103600Elucidating complex triplet-state dynamics in the model system isopropylthioxanthoneNikolaos Liaros0Sandra A. Gutierrez Razo1Matthew D. Thum2Hannah M. Ogden3Andrea N. Zeppuhar4Steven Wolf5Tommaso Baldacchini6Matthew J. Kelley7John S. Petersen8Daniel E. Falvey9Amy S. Mullin10John T. Fourkas11Department of Chemistry & Biochemistry, University of Maryland, College Park, MD 20742, USADepartment of Chemistry & Biochemistry, University of Maryland, College Park, MD 20742, USADepartment of Chemistry & Biochemistry, University of Maryland, College Park, MD 20742, USADepartment of Chemistry & Biochemistry, University of Maryland, College Park, MD 20742, USADepartment of Chemistry & Biochemistry, University of Maryland, College Park, MD 20742, USADepartment of Chemistry & Biochemistry, University of Maryland, College Park, MD 20742, USANewport Corporation, 1791 Deere Avenue, Irvine, CA 92606, USANewport Corporation, 1791 Deere Avenue, Irvine, CA 92606, USADepartment of Chemistry & Biochemistry, University of Maryland, College Park, MD 20742, USA; imec, Kapeldreef 75, 3001 Leuven, BelgiumDepartment of Chemistry & Biochemistry, University of Maryland, College Park, MD 20742, USADepartment of Chemistry & Biochemistry, University of Maryland, College Park, MD 20742, USADepartment of Chemistry & Biochemistry, University of Maryland, College Park, MD 20742, USA; Institute for Physical Science & Technology, University of Maryland, College Park, MD 20742, USA; Maryland Quantum Materials Center, University of Maryland, College Park, MD 20742, USA; Maryland NanoCenter, University of Maryland, College Park, MD 20742, USA; Corresponding authorSummary: We introduce techniques for probing the dynamics of triplet states. We employ these tools, along with conventional techniques, to develop a detailed understanding of a complex chemical system: a negative-tone, radical photoresist for multiphoton absorption polymerization in which isopropylthioxanthone (ITX) is the photoinitiator. This work reveals that the same color of light used for the 2-photon excitation of ITX, leading to population of the triplet manifold through intersystem crossing, also depletes this triplet population via linear absorption followed by reverse intersystem crossing (RISC). Using spectroscopic tools and kinetic modeling, we identify the reactive triplet state and a non-reactive reservoir triplet state. We present compelling evidence that the deactivation channel involves RISC from an excited triplet state to a highly vibrationally excited level of the electronic ground state. The work described here offers the enticing possibility of understanding, and ultimately controlling, the photochemistry and photophysics of a broad range of triplet processes.http://www.sciencedirect.com/science/article/pii/S2589004221015704ChemistryTheoretical photophysicsNonlinear optics |
| spellingShingle | Nikolaos Liaros Sandra A. Gutierrez Razo Matthew D. Thum Hannah M. Ogden Andrea N. Zeppuhar Steven Wolf Tommaso Baldacchini Matthew J. Kelley John S. Petersen Daniel E. Falvey Amy S. Mullin John T. Fourkas Elucidating complex triplet-state dynamics in the model system isopropylthioxanthone iScience Chemistry Theoretical photophysics Nonlinear optics |
| title | Elucidating complex triplet-state dynamics in the model system isopropylthioxanthone |
| title_full | Elucidating complex triplet-state dynamics in the model system isopropylthioxanthone |
| title_fullStr | Elucidating complex triplet-state dynamics in the model system isopropylthioxanthone |
| title_full_unstemmed | Elucidating complex triplet-state dynamics in the model system isopropylthioxanthone |
| title_short | Elucidating complex triplet-state dynamics in the model system isopropylthioxanthone |
| title_sort | elucidating complex triplet state dynamics in the model system isopropylthioxanthone |
| topic | Chemistry Theoretical photophysics Nonlinear optics |
| url | http://www.sciencedirect.com/science/article/pii/S2589004221015704 |
| work_keys_str_mv | AT nikolaosliaros elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone AT sandraagutierrezrazo elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone AT matthewdthum elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone AT hannahmogden elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone AT andreanzeppuhar elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone AT stevenwolf elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone AT tommasobaldacchini elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone AT matthewjkelley elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone AT johnspetersen elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone AT danielefalvey elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone AT amysmullin elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone AT johntfourkas elucidatingcomplextripletstatedynamicsinthemodelsystemisopropylthioxanthone |