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Title: Visible-Light-Driven Triplet Sensitization of Polycyclic Aromatic Hydrocarbons Using Thionated Perinones

Abstract

Metal-free chromophores that efficiently generate triplet excited states represent enticing alternatives with respect to transition metal-containing photosensitizers, such as those featuring metal-to-ligand charge transfer excited states. Yet, such molecular constructs have remained underexplored due to the unclear relationship(s) between molecular structure and efficient/rapid intersystem crossing. In this regard, we present a series of three thionated perinone chromophores serving as a newly conceived class of heavy metal-free triplet photosensitizers. We demonstrate that thionation of the lone C=O substituent in each highly fluorescent perinone imparts red-shifted absorbance bands that maintain intense extinction coefficients across the visible spectrum, as well as unusually efficient triplet excited state formation as inferred from the measured singlet O2 quantum yields at 1270 nm (ΦΔ = 0.78–1.0). Electronic structure calculations revealed the emergence of a low energy S1 (n → π*) excited state in the proximity of a slightly higher energy S2 (π → π*) excited state. The distinct character in each of the two lowest-lying singlet state manifolds resulted in the energetic inversion of the corresponding triplet excited states due to differences in electron exchange interactions. Rapid S1 → T1 intersystem crossing was thereby facilitated in this manner through spin–orbit coupling as predicted by the El Sayedmore » rules. The lifetimes of the resultant triplet excited states persisted into the microsecond time regime, as measured by transient absorbance spectroscopy, enabling effective bimolecular triplet sensitization of some common polycyclic aromatic hydrocarbons. The synthetically facile interchange of a single O atom to an S atom in the investigated perinones resulted in marked changes to their photophysical properties, namely, conversion of dominant singlet state fluorescence in the former to long-lived triplet excited states in the latter. The combined results suggest a general strategy for accessing long-lived triplet excited states in organic chromophores featuring a lone C=O moiety residing within its structure, valuable for the design of metal-free triplet photosensitizers.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]
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  1. North Carolina State Univ., Raleigh, NC (United States)
  2. North Carolina State Univ., Raleigh, NC (United States); United States Air Force Academy, Colorado Springs, CO (United States)
Publication Date:
Research Org.:
North Carolina State University, Raleigh, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Contributing Org.:
Air Force Institute of Technology (AFIT)
OSTI Identifier:
1633647
Grant/Contract Number:  
SC0011979; CHE-1665033
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 11; Journal Issue: 13; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Palmer, Jonathan R., Wells, Kaylee A., Yarnell, James E., Favale, Joseph M., and Castellano, Felix N. Visible-Light-Driven Triplet Sensitization of Polycyclic Aromatic Hydrocarbons Using Thionated Perinones. United States: N. p., 2020. Web. doi:10.1021/acs.jpclett.0c01634.
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Palmer, Jonathan R., Wells, Kaylee A., Yarnell, James E., Favale, Joseph M., & Castellano, Felix N. Visible-Light-Driven Triplet Sensitization of Polycyclic Aromatic Hydrocarbons Using Thionated Perinones. United States. https://doi.org/10.1021/acs.jpclett.0c01634
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Palmer, Jonathan R., Wells, Kaylee A., Yarnell, James E., Favale, Joseph M., and Castellano, Felix N. Tue . "Visible-Light-Driven Triplet Sensitization of Polycyclic Aromatic Hydrocarbons Using Thionated Perinones". United States. https://doi.org/10.1021/acs.jpclett.0c01634. https://www.osti.gov/servlets/purl/1633647.
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@article{osti_1633647,
title = {Visible-Light-Driven Triplet Sensitization of Polycyclic Aromatic Hydrocarbons Using Thionated Perinones},
author = {Palmer, Jonathan R. and Wells, Kaylee A. and Yarnell, James E. and Favale, Joseph M. and Castellano, Felix N.},
abstractNote = {Metal-free chromophores that efficiently generate triplet excited states represent enticing alternatives with respect to transition metal-containing photosensitizers, such as those featuring metal-to-ligand charge transfer excited states. Yet, such molecular constructs have remained underexplored due to the unclear relationship(s) between molecular structure and efficient/rapid intersystem crossing. In this regard, we present a series of three thionated perinone chromophores serving as a newly conceived class of heavy metal-free triplet photosensitizers. We demonstrate that thionation of the lone C=O substituent in each highly fluorescent perinone imparts red-shifted absorbance bands that maintain intense extinction coefficients across the visible spectrum, as well as unusually efficient triplet excited state formation as inferred from the measured singlet O2 quantum yields at 1270 nm (ΦΔ = 0.78–1.0). Electronic structure calculations revealed the emergence of a low energy S1 (n → π*) excited state in the proximity of a slightly higher energy S2 (π → π*) excited state. The distinct character in each of the two lowest-lying singlet state manifolds resulted in the energetic inversion of the corresponding triplet excited states due to differences in electron exchange interactions. Rapid S1 → T1 intersystem crossing was thereby facilitated in this manner through spin–orbit coupling as predicted by the El Sayed rules. The lifetimes of the resultant triplet excited states persisted into the microsecond time regime, as measured by transient absorbance spectroscopy, enabling effective bimolecular triplet sensitization of some common polycyclic aromatic hydrocarbons. The synthetically facile interchange of a single O atom to an S atom in the investigated perinones resulted in marked changes to their photophysical properties, namely, conversion of dominant singlet state fluorescence in the former to long-lived triplet excited states in the latter. The combined results suggest a general strategy for accessing long-lived triplet excited states in organic chromophores featuring a lone C=O moiety residing within its structure, valuable for the design of metal-free triplet photosensitizers.},
doi = {10.1021/acs.jpclett.0c01634},
journal = {Journal of Physical Chemistry Letters},
number = 13,
volume = 11,
place = {United States},
year = {Tue Jun 09 00:00:00 EDT 2020},
month = {Tue Jun 09 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acs.jpclett.0c01634
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