Bright, Modular, and Switchable Near-Infrared II Emission from Compact Tetrathiafulvalene-Based Diradicaloid Complexes

Lauren E. McNamara; Jan Niklas Boyn; Christopher Melnychuk; Sophie W. Anferov; David A. Mazziotti; Richard D. Schaller; John S. Anderson

doi:10.1021/jacs.2c04976

Bright, Modular, and Switchable Near-Infrared II Emission from Compact Tetrathiafulvalene-Based Diradicaloid Complexes

Lauren E. McNamara, Jan Niklas Boyn, Christopher Melnychuk, Sophie W. Anferov, David A. Mazziotti, Richard D. Schaller, John S. Anderson^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Near-infrared (NIR)-emitting molecules are promising candidates for biological sensing and imaging applications; however, many NIR dyes are large conjugated systems which frequently have issues with stability, solubility, and tunability. Here, we report a novel class of compact and tunable fluorescent diradicaloid complexes which are air-, water-, light-, and temperature-stable. These properties arise from a compressed πmanifold which promotes an intense ligand-centered π-πtransition in the NIR II (1000-1700 nm) region and which subsequently emits at ∼1200 nm. This emission is among the brightest known for monomolecular lumiphores with deep NIR II (>1100 nm) emission, nearly an order of magnitude brighter than the commercially available NIR II dye IR 26. Furthermore, this fluorescence is electrochemically sensitive, with efficient switching upon addition of redox agents. The brightness, stability, and modularity of this system distinguish it as a promising candidate for the development of new technologies built around NIR emission.

Original language	English (US)
Pages (from-to)	16447-16455
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	144
Issue number	36
DOIs	https://doi.org/10.1021/jacs.2c04976
State	Published - Sep 14 2022

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.2c04976

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@article{965d30ca9a134db3b801106de6a62702,

title = "Bright, Modular, and Switchable Near-Infrared II Emission from Compact Tetrathiafulvalene-Based Diradicaloid Complexes",

abstract = "Near-infrared (NIR)-emitting molecules are promising candidates for biological sensing and imaging applications; however, many NIR dyes are large conjugated systems which frequently have issues with stability, solubility, and tunability. Here, we report a novel class of compact and tunable fluorescent diradicaloid complexes which are air-, water-, light-, and temperature-stable. These properties arise from a compressed πmanifold which promotes an intense ligand-centered π-πtransition in the NIR II (1000-1700 nm) region and which subsequently emits at ∼1200 nm. This emission is among the brightest known for monomolecular lumiphores with deep NIR II (>1100 nm) emission, nearly an order of magnitude brighter than the commercially available NIR II dye IR 26. Furthermore, this fluorescence is electrochemically sensitive, with efficient switching upon addition of redox agents. The brightness, stability, and modularity of this system distinguish it as a promising candidate for the development of new technologies built around NIR emission.",

author = "McNamara, {Lauren E.} and Boyn, {Jan Niklas} and Christopher Melnychuk and Anferov, {Sophie W.} and Mazziotti, {David A.} and Schaller, {Richard D.} and Anderson, {John S.}",

note = "Funding Information: Part of this work was performed at the Soft Matter Characterization Facility at the Pritzker School of Molecular Engineering at the University of Chicago. J.S.A. and D.A.M. gratefully acknowledge support for this work from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under the grant DE-SC0019215. J.S.A. also gratefully acknowledges support from the 3M corporation through an NTFA, the Army Research Office under the grant W911NF-20-1-0091, and from a Dreyfus Teacher-Scholar Award (TC-21-064). This work was supported by the Chicago MRSEC, which is funded by NSF through the grant DMR-1420709. D.A.M. also gratefully acknowledges support from the ACS Petroleum Research Fund grant no. PRF no. 61644-ND6 and the U. S. National Science Foundation grant no. CHE-1565638. This work was performed, in part, at the Center for Nanoscale Materials, a DOE Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-06CH11357. Jiaze Xie, Libai Huang, Galina Grechishnikova, and Sarath Santhakumar are thanked for helpful discussions. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

month = sep,

day = "14",

doi = "10.1021/jacs.2c04976",

language = "English (US)",

volume = "144",

pages = "16447--16455",

journal = "Journal of the American Chemical Society",

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T1 - Bright, Modular, and Switchable Near-Infrared II Emission from Compact Tetrathiafulvalene-Based Diradicaloid Complexes

AU - McNamara, Lauren E.

AU - Boyn, Jan Niklas

AU - Melnychuk, Christopher

AU - Anferov, Sophie W.

AU - Mazziotti, David A.

AU - Schaller, Richard D.

AU - Anderson, John S.

N1 - Funding Information: Part of this work was performed at the Soft Matter Characterization Facility at the Pritzker School of Molecular Engineering at the University of Chicago. J.S.A. and D.A.M. gratefully acknowledge support for this work from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under the grant DE-SC0019215. J.S.A. also gratefully acknowledges support from the 3M corporation through an NTFA, the Army Research Office under the grant W911NF-20-1-0091, and from a Dreyfus Teacher-Scholar Award (TC-21-064). This work was supported by the Chicago MRSEC, which is funded by NSF through the grant DMR-1420709. D.A.M. also gratefully acknowledges support from the ACS Petroleum Research Fund grant no. PRF no. 61644-ND6 and the U. S. National Science Foundation grant no. CHE-1565638. This work was performed, in part, at the Center for Nanoscale Materials, a DOE Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-06CH11357. Jiaze Xie, Libai Huang, Galina Grechishnikova, and Sarath Santhakumar are thanked for helpful discussions. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/9/14

Y1 - 2022/9/14

N2 - Near-infrared (NIR)-emitting molecules are promising candidates for biological sensing and imaging applications; however, many NIR dyes are large conjugated systems which frequently have issues with stability, solubility, and tunability. Here, we report a novel class of compact and tunable fluorescent diradicaloid complexes which are air-, water-, light-, and temperature-stable. These properties arise from a compressed πmanifold which promotes an intense ligand-centered π-πtransition in the NIR II (1000-1700 nm) region and which subsequently emits at ∼1200 nm. This emission is among the brightest known for monomolecular lumiphores with deep NIR II (>1100 nm) emission, nearly an order of magnitude brighter than the commercially available NIR II dye IR 26. Furthermore, this fluorescence is electrochemically sensitive, with efficient switching upon addition of redox agents. The brightness, stability, and modularity of this system distinguish it as a promising candidate for the development of new technologies built around NIR emission.

AB - Near-infrared (NIR)-emitting molecules are promising candidates for biological sensing and imaging applications; however, many NIR dyes are large conjugated systems which frequently have issues with stability, solubility, and tunability. Here, we report a novel class of compact and tunable fluorescent diradicaloid complexes which are air-, water-, light-, and temperature-stable. These properties arise from a compressed πmanifold which promotes an intense ligand-centered π-πtransition in the NIR II (1000-1700 nm) region and which subsequently emits at ∼1200 nm. This emission is among the brightest known for monomolecular lumiphores with deep NIR II (>1100 nm) emission, nearly an order of magnitude brighter than the commercially available NIR II dye IR 26. Furthermore, this fluorescence is electrochemically sensitive, with efficient switching upon addition of redox agents. The brightness, stability, and modularity of this system distinguish it as a promising candidate for the development of new technologies built around NIR emission.

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 36

ER -

Bright, Modular, and Switchable Near-Infrared II Emission from Compact Tetrathiafulvalene-Based Diradicaloid Complexes

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CCDC 2171696: Experimental Crystal Structure Determination

CCDC 2171695: Experimental Crystal Structure Determination

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Bright, Modular, and Switchable Near-Infrared II Emission from Compact Tetrathiafulvalene-Based Diradicaloid Complexes

Abstract

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CCDC 2171697: Experimental Crystal Structure Determination

CCDC 2171696: Experimental Crystal Structure Determination

CCDC 2171695: Experimental Crystal Structure Determination

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