Thermally Controlled Exciplex Fluorescence in a Dynamic Homo[2]catenane

Amine Garci; Arthur H.G. David; Laura Le Bras; Marco Ovalle; Seifallah Abid; Ryan M. Young; Wenqi Liu; Chandra S. Azad; Paige J. Brown; Michael R. Wasielewski; J. Fraser Stoddart

doi:10.1021/jacs.2c10591

Thermally Controlled Exciplex Fluorescence in a Dynamic Homo[2]catenane

Amine Garci, Arthur H.G. David, Laura Le Bras, Marco Ovalle, Seifallah Abid, Ryan M. Young, Wenqi Liu, Chandra S. Azad, Paige J. Brown, Michael R. Wasielewski, J. Fraser Stoddart^*

^*Corresponding author for this work

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

Abstract

Motion-induced change in emission (MICE) is a phenomenon that can be employed to develop various types of probes, including temperature and viscosity sensors. Although MICE, arising from the conformational motion in particular compounds, has been studied extensively, this phenomenon has not been investigated in depth in mechanically interlocked molecules (MIMs) undergoing coconformational changes. Herein, we report the investigation of a thermoresponsive dynamic homo[2]catenane incorporating pyrene units and displaying relative circumrotational motions of its cyclophanes as evidenced by variable-temperature ¹H NMR spectroscopy and supported by its visualization through molecular dynamics simulations and quantum mechanics calculations. The relative coconformational motions induce a significant change in the fluorescence emission of the homo[2]catenane upon changes in temperature compared with its component cyclophanes. This variation in the exciplex emission of the homo[2]catenane is reversible as demonstrated by four complete cooling and heating cycles. This research opens up possibilities of using the coconformational changes in MIMs-based chromophores for probing fluctuations in temperature which could lead to applications in biomedicine or materials science.

Original language	English (US)
Pages (from-to)	23551-23559
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	144
Issue number	51
DOIs	https://doi.org/10.1021/jacs.2c10591
State	Published - Dec 28 2022

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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@article{5ef4b56be5c94f48b9520e157bbd3438,

title = "Thermally Controlled Exciplex Fluorescence in a Dynamic Homo[2]catenane",

abstract = "Motion-induced change in emission (MICE) is a phenomenon that can be employed to develop various types of probes, including temperature and viscosity sensors. Although MICE, arising from the conformational motion in particular compounds, has been studied extensively, this phenomenon has not been investigated in depth in mechanically interlocked molecules (MIMs) undergoing coconformational changes. Herein, we report the investigation of a thermoresponsive dynamic homo[2]catenane incorporating pyrene units and displaying relative circumrotational motions of its cyclophanes as evidenced by variable-temperature 1H NMR spectroscopy and supported by its visualization through molecular dynamics simulations and quantum mechanics calculations. The relative coconformational motions induce a significant change in the fluorescence emission of the homo[2]catenane upon changes in temperature compared with its component cyclophanes. This variation in the exciplex emission of the homo[2]catenane is reversible as demonstrated by four complete cooling and heating cycles. This research opens up possibilities of using the coconformational changes in MIMs-based chromophores for probing fluctuations in temperature which could lead to applications in biomedicine or materials science.",

author = "Amine Garci and David, {Arthur H.G.} and {Le Bras}, Laura and Marco Ovalle and Seifallah Abid and Young, {Ryan M.} and Wenqi Liu and Azad, {Chandra S.} and Brown, {Paige J.} and Wasielewski, {Michael R.} and Stoddart, {J. Fraser}",

note = "Funding Information: The authors thank Northwestern University for their continued support of this research. The authors acknowledge the Integrated Molecular Structure Education and Research Center (IMSERC) at NU for providing access to equipment for the experiments. L.L.B. would like to thank the supercomputer facilities of the M{\'e}socentre de calcul de Franche-Comt{\'e}. This project was also supported by the National Science Foundation under Grant Number DMR-2003739 (M.R.W., R.M.Y., P.J.B.). The authors thank Dr. Yuyang Wu for his assistance on VT H NMR measurements and Dr. Masoud Kazem-Rostami for helping in taking the pictures with the camera of his mobile phone, of the variable temperature fluorescence experiment performed by A.G. 1 Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

month = dec,

day = "28",

doi = "10.1021/jacs.2c10591",

language = "English (US)",

volume = "144",

pages = "23551--23559",

journal = "Journal of the American Chemical Society",

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publisher = "American Chemical Society",

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T1 - Thermally Controlled Exciplex Fluorescence in a Dynamic Homo[2]catenane

AU - Garci, Amine

AU - David, Arthur H.G.

AU - Le Bras, Laura

AU - Ovalle, Marco

AU - Abid, Seifallah

AU - Young, Ryan M.

AU - Liu, Wenqi

AU - Azad, Chandra S.

AU - Brown, Paige J.

AU - Wasielewski, Michael R.

AU - Stoddart, J. Fraser

N1 - Funding Information: The authors thank Northwestern University for their continued support of this research. The authors acknowledge the Integrated Molecular Structure Education and Research Center (IMSERC) at NU for providing access to equipment for the experiments. L.L.B. would like to thank the supercomputer facilities of the Mésocentre de calcul de Franche-Comté. This project was also supported by the National Science Foundation under Grant Number DMR-2003739 (M.R.W., R.M.Y., P.J.B.). The authors thank Dr. Yuyang Wu for his assistance on VT H NMR measurements and Dr. Masoud Kazem-Rostami for helping in taking the pictures with the camera of his mobile phone, of the variable temperature fluorescence experiment performed by A.G. 1 Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/12/28

Y1 - 2022/12/28

N2 - Motion-induced change in emission (MICE) is a phenomenon that can be employed to develop various types of probes, including temperature and viscosity sensors. Although MICE, arising from the conformational motion in particular compounds, has been studied extensively, this phenomenon has not been investigated in depth in mechanically interlocked molecules (MIMs) undergoing coconformational changes. Herein, we report the investigation of a thermoresponsive dynamic homo[2]catenane incorporating pyrene units and displaying relative circumrotational motions of its cyclophanes as evidenced by variable-temperature 1H NMR spectroscopy and supported by its visualization through molecular dynamics simulations and quantum mechanics calculations. The relative coconformational motions induce a significant change in the fluorescence emission of the homo[2]catenane upon changes in temperature compared with its component cyclophanes. This variation in the exciplex emission of the homo[2]catenane is reversible as demonstrated by four complete cooling and heating cycles. This research opens up possibilities of using the coconformational changes in MIMs-based chromophores for probing fluctuations in temperature which could lead to applications in biomedicine or materials science.

AB - Motion-induced change in emission (MICE) is a phenomenon that can be employed to develop various types of probes, including temperature and viscosity sensors. Although MICE, arising from the conformational motion in particular compounds, has been studied extensively, this phenomenon has not been investigated in depth in mechanically interlocked molecules (MIMs) undergoing coconformational changes. Herein, we report the investigation of a thermoresponsive dynamic homo[2]catenane incorporating pyrene units and displaying relative circumrotational motions of its cyclophanes as evidenced by variable-temperature 1H NMR spectroscopy and supported by its visualization through molecular dynamics simulations and quantum mechanics calculations. The relative coconformational motions induce a significant change in the fluorescence emission of the homo[2]catenane upon changes in temperature compared with its component cyclophanes. This variation in the exciplex emission of the homo[2]catenane is reversible as demonstrated by four complete cooling and heating cycles. This research opens up possibilities of using the coconformational changes in MIMs-based chromophores for probing fluctuations in temperature which could lead to applications in biomedicine or materials science.

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U2 - 10.1021/jacs.2c10591

DO - 10.1021/jacs.2c10591

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SN - 0002-7863

VL - 144

SP - 23551

EP - 23559

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 51

ER -

Thermally Controlled Exciplex Fluorescence in a Dynamic Homo[2]catenane

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