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Nano Research 2021, 14(12): 4563-4568 https://doi.org/10.1007/s12274-021-3374-3
Research Article | Issue | Published: 03 March 2021

Construction of poly-naphthalocyanine linked by [4]-radialene-like structures on silver surfaces

Show Author's Information Rongting Wu1,§,†,  De-Liang Bao1,§,  Linghao Yan1,  Junhai Ren1,  Yanfang Zhang1,  Qi Zheng1,  Ye-Liang Wang1,  Qing Huan1( ),  Shixuan Du1,2,3( ),  Hong-Jun Gao1,2
Institute of Physics & University of Chinese Academy of Sciences, Chinese Academy of SciencesBeijing100190China
CAS Center for Excellence in Topological Quantum Computation, Chinese Academy of SciencesBeijing100190China
Songshan Lake Materials LaboratoryDongguan523808China

§ Rongting Wu and De-Liang Bao contributed equally to this work.

Keywords:
density functional theory calculation, polymerization, scanning tunneling microscope, naphthalocyanine, π-interaction extension
Topics:
Atomic physics
Cite this article:
Wu R, Bao D-L, Yan L, et al. Construction of poly-naphthalocyanine linked by [4]-radialene-like structures on silver surfaces. Nano Research, 2021, 14(12): 4563-4568. https://doi.org/10.1007/s12274-021-3374-3
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Abstract Full text About this article

Cyclic-conjugated linkages between planar-macrocyclic molecules contribute to the robustness of the two-dimensional (2D) polymerization and extension of π-interactions. The fabrication of such linkages in 2D polymers remains challenging. Combining scanning tunneling microscope (STM) measurements and density functional theory (DFT) calculations, we demonstrate a linear polymerization of metal-free naphthalocyanine (NPc) molecules with [4]-radialene-like linkages on silver surfaces. Experimentally, by depositing NPc molecules on the Ag(110) surface and subsequent annealing up to 750 K, one-dimensional polymers are constructed along the [11(_)0] direction. High-resolution STM images show a stem-leaf-like feature. STM simulations based on a linear polymer of NPc molecules linked by four-membered carbon rings, [4]-radialene-like structure, agree well with the experimental observations. DFT calculations reveal that the polymerization process includes detaching two-terminal H atoms of NPc molecules along [11(_)0] direction, then bonding with a neighboring dehydrogenated NPc molecule by forming a four-membered ring. The dehydrogenation process can be promoted by on-surface impurities such as additional H atoms. Similar polymerizations have been achieved on Ag(111) surfaces in an amorphous way. Moreover, the energy gap of the NPc molecule decreases after linear polymerization, suggesting a red-shift for its optical absorption/scattering spectrum. Our study offers a new route to polymerize conjugated molecules with extended planar π-interactions.


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About this article

Construction of poly-naphthalocyanine linked by [4]-radialene-like structures on silver surfaces

Show Author's information Rongting Wu1,§,†, De-Liang Bao1,§, Linghao Yan1, Junhai Ren1, Yanfang Zhang1, Qi Zheng1, Ye-Liang Wang1, Qing Huan1( ), Shixuan Du1,2,3( ), Hong-Jun Gao1,2
Institute of Physics & University of Chinese Academy of Sciences, Chinese Academy of SciencesBeijing100190China
CAS Center for Excellence in Topological Quantum Computation, Chinese Academy of SciencesBeijing100190China
Songshan Lake Materials LaboratoryDongguan523808China

§ Rongting Wu and De-Liang Bao contributed equally to this work.

Abstract

Cyclic-conjugated linkages between planar-macrocyclic molecules contribute to the robustness of the two-dimensional (2D) polymerization and extension of π-interactions. The fabrication of such linkages in 2D polymers remains challenging. Combining scanning tunneling microscope (STM) measurements and density functional theory (DFT) calculations, we demonstrate a linear polymerization of metal-free naphthalocyanine (NPc) molecules with [4]-radialene-like linkages on silver surfaces. Experimentally, by depositing NPc molecules on the Ag(110) surface and subsequent annealing up to 750 K, one-dimensional polymers are constructed along the [11(_)0] direction. High-resolution STM images show a stem-leaf-like feature. STM simulations based on a linear polymer of NPc molecules linked by four-membered carbon rings, [4]-radialene-like structure, agree well with the experimental observations. DFT calculations reveal that the polymerization process includes detaching two-terminal H atoms of NPc molecules along [11(_)0] direction, then bonding with a neighboring dehydrogenated NPc molecule by forming a four-membered ring. The dehydrogenation process can be promoted by on-surface impurities such as additional H atoms. Similar polymerizations have been achieved on Ag(111) surfaces in an amorphous way. Moreover, the energy gap of the NPc molecule decreases after linear polymerization, suggesting a red-shift for its optical absorption/scattering spectrum. Our study offers a new route to polymerize conjugated molecules with extended planar π-interactions.

Keywords: density functional theory calculation, polymerization, scanning tunneling microscope, naphthalocyanine, π-interaction extension

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Publication history
Copyright
Acknowledgements

Publication history

Received: 01 December 2020
Revised: 21 January 2021
Accepted: 31 January 2021
Published: 03 March 2021
Issue date: December 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

We thank Prof. Werner Hofer and Prof. Sokrates T. Pantelides for helpful discussions and suggestions. This work was financially supported by the National Key Research and Development Program of China (No. 2016YFA0202300), the National Natural Science Foundation of China (Nos. 61888102 and 61725107), Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB30000000), the International Partnership Program of Chinese Academy of Sciences (No. 112111KYSB20160061), and China Postdoctoral Science Foundation (No. 2018M641511). DFT computations were carried out at the National Supercomputing Center of Tianjin.

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