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

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:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [3];  [4]; ORCiD logo [5]; ORCiD logo [2];  [6]; ORCiD logo [7]; ORCiD logo [1]
  1. Univ. of South Florida, Tampa, FL (United States)
  2. Univ. of North Texas, Denton, TX (United States)
  3. Jilin Univ. (China)
  4. Univ. of South Florida, Tampa, FL (United States); Zhengzhou Univ. (China)
  5. Zhengzhou Univ. (China)
  6. Argonne National Lab. (ANL), Argonne, IL (United States); Old Dominion Univ., Norfolk, VA (United States)
  7. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
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.
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
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.
@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}
}

Journal Article:
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