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Title: Self-assembly directed one-step synthesis of [4]radialene on Cu(100) surfaces

Abstract

The synthetic challenges of radialenes have precluded their practical applications. Here, we report a one-step synthetic protocol of [4]radialene on a copper surface. High-resolution scanning tunneling microscopy measurements reveal that such catalytic reaction proceeds readily with high selectivity at the temperature below 120 K. First-principles calculations show that the reaction pathway is characterized by firstly the cooperative inter-molecular hydrogen tautomerization and then the C–C bond formation. The feasibility of such cyclotetramerization reaction can be interpreted by the surface effect of Cu(100), which firstly plays an important role in directing the molecular assembly and then serves as an active catalyst in the hydrogen tautomerization and C–C coupling processes. This work presents not only a novel strategy to the scant number of synthetic methods to produce [4]radialenes via a novel [1 + 1 + 1 + 1] reaction pathway, but also a successful example of C–C bond coupling reactions guided by the surface-induced C–H/π assembly.

Authors:
 [1];  [2]; ORCiD logo [1];  [3];  [4];  [5]; ORCiD logo [1];  [1];  [6]
  1. Soochow Univ., Suzhou (China). Inst. of Functional Nano & Soft Materials (FUNSOM). Jiangsu Key Lab. for Carbon-Based Functional Materials & Devices
  2. Shaanxi Normal Univ., Xi’an (China). School of Physics and Information Technology
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences. Computational Sciences and Engineering Division
  4. National Center for Nanoscience and Technology, Beijing (China). CAS Key Lab. of Standardization and Measurement for Nanotechnology. CAS Center for Excellence in Nanoscience
  5. National Center for Nanoscience and Technology, Beijing (China). CAS Key Lab. of Standardization and Measurement for Nanotechnology. CAS Center for Excellence in Nanoscience; Univ. of Chinese Academy of Sciences, Beijing (China)
  6. Huazhong Univ. of Science and Technology, Wuhan (China). School of Physics
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Soochow Univ., Suzhou (China); National Center for Nanoscience and Technology, Beijing (China)
Sponsoring Org.:
USDOE Office of Science (SC); National Natural Science Foundation of China (NNSFC); Natural Science Foundation of Jiangsu Province (China); Major State Basic Research Development Program of China
OSTI Identifier:
1463979
Grant/Contract Number:  
AC05-00OR22725; 21622306; 91545127; 21790053; 21771134; 11574095; BK20140305; BK20150305; 2017YFA0205002; 2017YFA0204800; 2014CB932600
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; density functional theory; scanning probe microscopy; surface assembly

Citation Formats

Li, Qing, Gao, Jianzhi, Li, Youyong, Fuentes-Cabrera, Miguel, Liu, Mengxi, Qiu, Xiaohui, Lin, Haiping, Chi, Lifeng, and Pan, Minghu. Self-assembly directed one-step synthesis of [4]radialene on Cu(100) surfaces. United States: N. p., 2018. Web. doi:10.1038/s41467-018-05472-2.
Li, Qing, Gao, Jianzhi, Li, Youyong, Fuentes-Cabrera, Miguel, Liu, Mengxi, Qiu, Xiaohui, Lin, Haiping, Chi, Lifeng, & Pan, Minghu. Self-assembly directed one-step synthesis of [4]radialene on Cu(100) surfaces. United States. doi:10.1038/s41467-018-05472-2.
Li, Qing, Gao, Jianzhi, Li, Youyong, Fuentes-Cabrera, Miguel, Liu, Mengxi, Qiu, Xiaohui, Lin, Haiping, Chi, Lifeng, and Pan, Minghu. Mon . "Self-assembly directed one-step synthesis of [4]radialene on Cu(100) surfaces". United States. doi:10.1038/s41467-018-05472-2. https://www.osti.gov/servlets/purl/1463979.
@article{osti_1463979,
title = {Self-assembly directed one-step synthesis of [4]radialene on Cu(100) surfaces},
author = {Li, Qing and Gao, Jianzhi and Li, Youyong and Fuentes-Cabrera, Miguel and Liu, Mengxi and Qiu, Xiaohui and Lin, Haiping and Chi, Lifeng and Pan, Minghu},
abstractNote = {The synthetic challenges of radialenes have precluded their practical applications. Here, we report a one-step synthetic protocol of [4]radialene on a copper surface. High-resolution scanning tunneling microscopy measurements reveal that such catalytic reaction proceeds readily with high selectivity at the temperature below 120 K. First-principles calculations show that the reaction pathway is characterized by firstly the cooperative inter-molecular hydrogen tautomerization and then the C–C bond formation. The feasibility of such cyclotetramerization reaction can be interpreted by the surface effect of Cu(100), which firstly plays an important role in directing the molecular assembly and then serves as an active catalyst in the hydrogen tautomerization and C–C coupling processes. This work presents not only a novel strategy to the scant number of synthetic methods to produce [4]radialenes via a novel [1 + 1 + 1 + 1] reaction pathway, but also a successful example of C–C bond coupling reactions guided by the surface-induced C–H/π assembly.},
doi = {10.1038/s41467-018-05472-2},
journal = {Nature Communications},
number = ,
volume = 9,
place = {United States},
year = {2018},
month = {8}
}

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    On‐Surface Evolution of meso ‐Isomerism in Two‐Dimensional Supramolecular Assemblies
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    On‐Surface Evolution of meso ‐Isomerism in Two‐Dimensional Supramolecular Assemblies
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