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

doi:10.1038/s41467-018-05472-2

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

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:

Li, Qing ^[1] ; Gao, Jianzhi ^[2] ; ; Fuentes-Cabrera, Miguel ^[3] ; Liu, Mengxi ^[4] ; Qiu, Xiaohui ^[5] ; ; Chi, Lifeng ^[1] ; Pan, Minghu ^[6]

Soochow Univ., Suzhou (China). Inst. of Functional Nano & Soft Materials (FUNSOM). Jiangsu Key Lab. for Carbon-Based Functional Materials & Devices
Shaanxi Normal Univ., Xi’an (China). School of Physics and Information Technology
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences. Computational Sciences and Engineering Division
National Center for Nanoscience and Technology, Beijing (China). CAS Key Lab. of Standardization and Measurement for Nanotechnology. CAS Center for Excellence in Nanoscience
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)
Huazhong Univ. of Science and Technology, Wuhan (China). School of Physics

Publication Date:: 2018-08-06

Grant/Contract Number:: AC05-00OR22725; 21622306; 91545127; 21790053; 21771134; 11574095; BK20140305; BK20150305; 2017YFA0205002; 2017YFA0204800; 2014CB932600

Type:: Accepted Manuscript

Journal Name:: Nature Communications

Additional Journal Information:: Journal Volume: 9; Journal ID: ISSN 2041-1723

Publisher:: Nature Publishing Group

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

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; density functional theory; scanning probe microscopy; surface assembly

OSTI Identifier:: 1463979


                    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.,  
        Web.  doi:10.1038/s41467-018-05472-2.

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                    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.

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                    Li, Qing, Gao, Jianzhi, Li, Youyong, Fuentes-Cabrera, Miguel, Liu, Mengxi, Qiu, Xiaohui, Lin, Haiping, Chi, Lifeng, and Pan, Minghu. 2018.  
        "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.

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@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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Free Publicly Accessible Full Text
Accepted Manuscript (DOE)
Publisher's Version of Record
10.1038/s41467-018-05472-2
https://doi.org/10.1038/s41467-018-05472-2

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Generalized Gradient Approximation Made Simple
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Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
DOI: 10.1103/PhysRevLett.77.3865

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Kresse, G.; Joubert, D.
Physical Review B, Vol. 59, Issue 3, p. 1758-1775
DOI: 10.1103/PhysRevB.59.1758

Special points for Brillouin-zone integrations
journal, June 1976

Monkhorst, Hendrik J.; Pack, James D.
Physical Review B, Vol. 13, Issue 12, p. 5188-5192
DOI: 10.1103/PhysRevB.13.5188

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Kresse, G.; Furthmüller, J.
Physical Review B, Vol. 54, Issue 16, p. 11169-11186
DOI: 10.1103/PhysRevB.54.11169

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

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