Self-Assembly of Metallo-Supramolecules under Kinetic or Thermodynamic Control: Characterization of Positional Isomers Using Scanning Tunneling Spectroscopy

doi:https://doi.org/10.1021/jacs.0c03459

Title: Self-Assembly of Metallo-Supramolecules under Kinetic or Thermodynamic Control: Characterization of Positional Isomers Using Scanning Tunneling Spectroscopy

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Abstract

Coordination-driven self-assembly has been extensively employed to construct a variety of discrete structures as a bottom-up strategy. However, mechanistic understanding regarding whether self-assembly is under kinetic or thermodynamic control is less explored. To date, such mechanistic investigation has been limited to distinct, assembled structures. It still remains a formidable challenge to study the kinetic and thermodynamic behavior of self-assembly systems with multiple assembled isomers due to the lack of characterization methods. Herein, we use a stepwise strategy which combined self-recognition and self-assembly processes to construct giant metallo-supramolecules with 8 positional isomers in solution. With the help of ultrahigh-vacuum, low-temperature scanning tunneling microscopy and scanning tunneling spectroscopy, we were able to unambiguously differentiate 14 isomers on the substrate which correspond to 8 isomers in solution. Through measurement of 162 structures, the experimental probability of each isomer was obtained and compared with the theoretical probability. Finally, such a comparison along with density functional theory (DFT) calculation suggested that although both kinetic and thermodynamic control existed in this self-assembly, the increased experimental probabilities of isomers compared to theoretical probabilities should be attributed to thermodynamic control.

Authors:

^[1];

^[1]; Gong, Lele ^[2];

^[3];

^[3]; Lu, Shuai ^[4];

^[5];

^[2]; Zhang, Yuan ^[6];

^[7];

^[1]

Univ. of South Florida, Tampa, FL (United States)
Univ. of North Texas, Denton, TX (United States)
Jilin Univ. (China)
Univ. of South Florida, Tampa, FL (United States); Zhengzhou Univ. (China)
Zhengzhou Univ. (China)
Argonne National Lab. (ANL), Argonne, IL (United States); Old Dominion Univ., Norfolk, VA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Publication Date:: 2020-04-20

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)

OSTI Identifier:: 1664385

Grant/Contract Number:: AC02-06CH11357; R01GM128037

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 142; Journal Issue: 21; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; isomers; STM; supramolecule; metallo-supramolecules; supramolecular isomerism; self-assembly; scanning tunneling microscopy; terpyridine

Citation Formats


                    Wang, Lei, Song, Bo, Li, Yiming, Gong, Lele, Jiang, Xin, Wang, Ming, Lu, Shuai, Hao, Xin-Qi, Xia, Zhenhai, Zhang, Yuan, Hla, Saw Wai, and Li, Xiaopeng. Self-Assembly of Metallo-Supramolecules under Kinetic or Thermodynamic Control: Characterization of Positional Isomers Using Scanning Tunneling Spectroscopy.  United States: N. p., 2020. 
        Web.  doi:10.1021/jacs.0c03459.

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                    Wang, Lei, Song, Bo, Li, Yiming, Gong, Lele, Jiang, Xin, Wang, Ming, Lu, Shuai, Hao, Xin-Qi, Xia, Zhenhai, Zhang, Yuan, Hla, Saw Wai, & Li, Xiaopeng. Self-Assembly of Metallo-Supramolecules under Kinetic or Thermodynamic Control: Characterization of Positional Isomers Using Scanning Tunneling Spectroscopy.  United States.  https://doi.org/10.1021/jacs.0c03459

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                    Wang, Lei, Song, Bo, Li, Yiming, Gong, Lele, Jiang, Xin, Wang, Ming, Lu, Shuai, Hao, Xin-Qi, Xia, Zhenhai, Zhang, Yuan, Hla, Saw Wai, and Li, Xiaopeng. Mon .  
        "Self-Assembly of Metallo-Supramolecules under Kinetic or Thermodynamic Control: Characterization of Positional Isomers Using Scanning Tunneling Spectroscopy".  United States.  https://doi.org/10.1021/jacs.0c03459.

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@article{osti_1664385,

  title        = {Self-Assembly of Metallo-Supramolecules under Kinetic or Thermodynamic Control: Characterization of Positional Isomers Using Scanning Tunneling Spectroscopy},

  author       = {Wang, Lei and Song, Bo and Li, Yiming and Gong, Lele and Jiang, Xin and Wang, Ming and Lu, Shuai and Hao, Xin-Qi and Xia, Zhenhai and Zhang, Yuan and Hla, Saw Wai and Li, Xiaopeng},

  abstractNote = {Coordination-driven self-assembly has been extensively employed to construct a variety of discrete structures as a bottom-up strategy. However, mechanistic understanding regarding whether self-assembly is under kinetic or thermodynamic control is less explored. To date, such mechanistic investigation has been limited to distinct, assembled structures. It still remains a formidable challenge to study the kinetic and thermodynamic behavior of self-assembly systems with multiple assembled isomers due to the lack of characterization methods. Herein, we use a stepwise strategy which combined self-recognition and self-assembly processes to construct giant metallo-supramolecules with 8 positional isomers in solution. With the help of ultrahigh-vacuum, low-temperature scanning tunneling microscopy and scanning tunneling spectroscopy, we were able to unambiguously differentiate 14 isomers on the substrate which correspond to 8 isomers in solution. Through measurement of 162 structures, the experimental probability of each isomer was obtained and compared with the theoretical probability. Finally, such a comparison along with density functional theory (DFT) calculation suggested that although both kinetic and thermodynamic control existed in this self-assembly, the increased experimental probabilities of isomers compared to theoretical probabilities should be attributed to thermodynamic control.},

  doi          = {10.1021/jacs.0c03459},

  url          = {https://www.osti.gov/biblio/1664385},
  journal      = {Journal of the American Chemical Society},

  issn         = {0002-7863},

  number       = 21,

  volume       = 142,

  place        = {United States},

  year         = {2020},

  month        = {4}

}

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