Photochemical spin-state control of binding configuration for tailoring organic color center emission in carbon nanotubes

Zheng, Yu; Han, Yulun; Weight, Braden M.; Lin, Zhiwei; Gifford, Brendan J.; Zheng, Ming; Kilin, Dmitri; Kilina, Svetlana; Doorn, Stephen K.; Htoon, Han; Tretiak, Sergei

doi:10.1038/s41467-022-31921-0

Photochemical spin-state control of binding configuration for tailoring organic color center emission in carbon nanotubes

Journal Article · Mon Aug 01 00:00:00 EDT 2022 · Nature Communications

DOI:https://doi.org/10.1038/s41467-022-31921-0· OSTI ID:1879167

Zheng, Yu; Han, Yulun; Weight, Braden M.; Lin, Zhiwei; Gifford, Brendan J.; ; ; Kilina, Svetlana; Doorn, Stephen K.; ;

Abstract

Incorporating fluorescent quantum defects in the sidewalls of semiconducting single-wall carbon nanotubes (SWCNTs) through chemical reaction is an emerging route to predictably modify nanotube electronic structures and develop advanced photonic functionality. Applications such as room-temperature single-photon emission and high-contrast bio-imaging have been advanced through aryl-functionalized SWCNTs, in which the binding configurations of the aryl group define the energies of the emitting states. However, the chemistry of binding with atomic precision at the single-bond level and tunable control over the binding configurations are yet to be achieved. Here, we explore recently reported photosynthetic protocol and find that it can control chemical binding configurations of quantum defects, which are often referred to as organic color centers, through the spin multiplicity of photoexcited intermediates. Specifically, photoexcited aromatics react with SWCNT sidewalls to undergo a singlet-state pathway in the presence of dissolved oxygen, leading to ortho binding configurations of the aryl group on the nanotube. In contrast, the oxygen-free photoreaction activates previously inaccessible para configurations through a triplet-state mechanism. These experimental results are corroborated by first principles simulations. Such spin-selective photochemistry diversifies SWCNT emission tunability by controlling the morphology of the emitting sites.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); North Dakota State University, Fargo, ND (United States)

Sponsoring Organization:: National Institute of Standards and Technology (NIST); National Science Foundation (NSF); USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: 89233218CNA000001; AC02-05CH11231; SC0021287

OSTI ID:: 1879167

Alternate ID(s):: OSTI ID: 2406556
OSTI ID: 2483987
OSTI ID: 1904260

Report Number(s):: LA-UR--21-25882; 4439; PII: 31921

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 13; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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Photochemical spin-state control of binding configuration for tailoring organic color center emission in carbon nanotubes

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