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Title: Long-Lived Excited State in a Solubilized Graphene Nanoribbon

Abstract

Graphene nanoribbons have excellent light-absorbing properties, but often exhibit short excited-state lifetimes that prevent their applications in photocatalysis. Here, we report a long-lived charge-transfer triplet excited state in a well solubilized, chlorinated graphene nanoribbon (Cl-GNR) with edges modified by bipyrimidine (bpm) moieties. The photophysical behavior of Cl-GNR was observed and characterized by steady-state UV-vis absorption and emission spectroscopy, transient absorption spectroscopy on the ps-ms timescale, and density functional theory (DFT) calculations. In this work, both the Cl-GNR and its monomeric subunit, chlorinated graphene quantum dot (Cl-GQD), were synthesized using bottom-up techniques to produce the H- analogs of the compounds followed by edge-chlorination to achieve soluble products. The absorption spectra of Cl-GQD and Cl-GNR appear in the UV-vis range with lowest-energy peaks at 375 and 600 nm, respectively. The excitons in Cl-GNR were found to exhibit charge-transfer character with the bpm edges serving as electron acceptors. DFT calculations indicate that the excitons are relatively localized, spreading over at most two monomeric units of the GNR. Transient absorption spectroscopy shows that singlet excited states of Cl-GQD and Cl-GNR undergo intersystem crossing with ~300 ps lifetime to form triplet states that last for 15.7 μs (Cl-GQD) and 106 μs (Cl-GNR). These properties, combinedmore » with the ability of the bpm sites to coordinate transition metals, make Cl-GNRs promising light-harvesting motifs for photocatalytic applications.« less

Authors:
 [1];  [1];  [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
  3. Univ. of Washington, Seattle, WA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1877685
Grant/Contract Number:  
AC02-06CH11357; 1954298
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 126; Journal Issue: 4; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Drummer, Matthew C., Weerasooriya, Ravindra B., Gupta, Nikita, Phelan, Brian T., Valentine, Andrew J. S., Cordones, Amy A., Li, Xiaosong, Chen, Lin X., and Glusac, Ksenija D. Long-Lived Excited State in a Solubilized Graphene Nanoribbon. United States: N. p., 2022. Web. doi:10.1021/acs.jpcc.1c10024.
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Drummer, Matthew C., Weerasooriya, Ravindra B., Gupta, Nikita, Phelan, Brian T., Valentine, Andrew J. S., Cordones, Amy A., Li, Xiaosong, Chen, Lin X., & Glusac, Ksenija D. Long-Lived Excited State in a Solubilized Graphene Nanoribbon. United States. https://doi.org/10.1021/acs.jpcc.1c10024
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Drummer, Matthew C., Weerasooriya, Ravindra B., Gupta, Nikita, Phelan, Brian T., Valentine, Andrew J. S., Cordones, Amy A., Li, Xiaosong, Chen, Lin X., and Glusac, Ksenija D. Mon . "Long-Lived Excited State in a Solubilized Graphene Nanoribbon". United States. https://doi.org/10.1021/acs.jpcc.1c10024. https://www.osti.gov/servlets/purl/1877685.
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@article{osti_1877685,
title = {Long-Lived Excited State in a Solubilized Graphene Nanoribbon},
author = {Drummer, Matthew C. and Weerasooriya, Ravindra B. and Gupta, Nikita and Phelan, Brian T. and Valentine, Andrew J. S. and Cordones, Amy A. and Li, Xiaosong and Chen, Lin X. and Glusac, Ksenija D.},
abstractNote = {Graphene nanoribbons have excellent light-absorbing properties, but often exhibit short excited-state lifetimes that prevent their applications in photocatalysis. Here, we report a long-lived charge-transfer triplet excited state in a well solubilized, chlorinated graphene nanoribbon (Cl-GNR) with edges modified by bipyrimidine (bpm) moieties. The photophysical behavior of Cl-GNR was observed and characterized by steady-state UV-vis absorption and emission spectroscopy, transient absorption spectroscopy on the ps-ms timescale, and density functional theory (DFT) calculations. In this work, both the Cl-GNR and its monomeric subunit, chlorinated graphene quantum dot (Cl-GQD), were synthesized using bottom-up techniques to produce the H- analogs of the compounds followed by edge-chlorination to achieve soluble products. The absorption spectra of Cl-GQD and Cl-GNR appear in the UV-vis range with lowest-energy peaks at 375 and 600 nm, respectively. The excitons in Cl-GNR were found to exhibit charge-transfer character with the bpm edges serving as electron acceptors. DFT calculations indicate that the excitons are relatively localized, spreading over at most two monomeric units of the GNR. Transient absorption spectroscopy shows that singlet excited states of Cl-GQD and Cl-GNR undergo intersystem crossing with ~300 ps lifetime to form triplet states that last for 15.7 μs (Cl-GQD) and 106 μs (Cl-GNR). These properties, combined with the ability of the bpm sites to coordinate transition metals, make Cl-GNRs promising light-harvesting motifs for photocatalytic applications.},
doi = {10.1021/acs.jpcc.1c10024},
journal = {Journal of Physical Chemistry. C},
number = 4,
volume = 126,
place = {United States},
year = {Mon Jan 24 00:00:00 EST 2022},
month = {Mon Jan 24 00:00:00 EST 2022}
}
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