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

Journal Article · · Nature Communications
 [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
+ Show Author Affiliations

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.

Research Organization:
National Center for Nanoscience and Technology, Beijing (China); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Soochow Univ., Suzhou (China)
Sponsoring Organization:
Major State Basic Research Development Program of China; National Natural Science Foundation of China (NSFC); Natural Science Foundation of Jiangsu Province (China); USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1463979
Journal Information:
Nature Communications, Journal Name: Nature Communications Vol. 9; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Two-Dimensional Hydrogen-Bonded Nanoarchitecture Composed of Rectangular 3,4,9,10-Perylenetetracarboxylic Diimide and Boomerang-Shaped Molecules Resulting from the Dissociation of 1,3,5-Tris(4-aminophenyl)benzene journal February 2020
Reaction selectivity of homochiral versus heterochiral intermolecular reactions of prochiral terminal alkynes on surfaces journal September 2019
Two‐Sidedness of Surface Reaction Mediation journal July 2019
On‐Surface Evolution of meso ‐Isomerism in Two‐Dimensional Supramolecular Assemblies journal June 2019
Atomic‐Scale Visualization of the Stepwise Metal‐Mediated Dehalogenative Cycloaddition Reaction Pathways: Competition between Radicals and Organometallic Intermediates journal October 2019
Identifying Multinuclear Organometallic Intermediates in On‐Surface [2+2] Cycloaddition Reactions journal October 2019
On‐Surface Evolution of meso ‐Isomerism in Two‐Dimensional Supramolecular Assemblies journal July 2019
Atomic‐Scale Visualization of the Stepwise Metal‐Mediated Dehalogenative Cycloaddition Reaction Pathways: Competition between Radicals and Organometallic Intermediates journal December 2019
Identifying Multinuclear Organometallic Intermediates in On‐Surface [2+2] Cycloaddition Reactions journal November 2019
Reaction selectivity of homochiral versus heterochiral intermolecular reactions of prochiral terminal alkynes on surfaces journal September 2019
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36 MATERIALS SCIENCE
density functional theory
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