Extending on-surface synthesis from 2D to 3D by cycloaddition with C60

Pengcheng Ding; Shaoshan Wang; Cristina Mattioli; Zhuo Li; Guoqiang Shi; Ye Sun; André Gourdon; Lev Kantorovich; Flemming Besenbacher; Federico Rosei; Miao Yu

doi:10.1038/s41467-023-41913-3

Extending on-surface synthesis from 2D to 3D by cycloaddition with C₆₀

Pengcheng Ding, Shaoshan Wang, Cristina Mattioli, Zhuo Li, Guoqiang Shi, Ye Sun, André Gourdon, Lev Kantorovich, Flemming Besenbacher, Federico Rosei, Miao Yu^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

As an efficient molecular engineering approach, on-surface synthesis (OSS) defines a special opportunity to investigate intermolecular coupling at the sub-molecular level and has delivered many appealing polymers. So far, all OSS is based on the lateral covalent bonding of molecular precursors within a single molecular layer; extending OSS from two to three dimensions is yet to be realized. Herein, we address this challenge by cycloaddition between C₆₀ and an aromatic compound. The C₆₀ layer is assembled on the well-defined molecular network, allowing appropriate molecular orbital hybridization. Upon thermal activation, covalent coupling perpendicular to the surface via [4 + 2] cycloaddition between C₆₀ and the phenyl ring of the molecule is realized; the resultant adduct shows frozen orientation and distinct sub-molecular feature at room temperature and further enables lateral covalent bonding via [2 + 2] cycloaddition. This work unlocks an unconventional route for bottom-up precise synthesis of three-dimensional covalently-bonded organic architectures/devices on surfaces.

Original language	English
Article number	6075
Journal	Nature Communications
Volume	14
Issue number	1
Early online date	28 Sept 2023
DOIs	https://doi.org/10.1038/s41467-023-41913-3
Publication status	Published - Dec 2023

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title = "Extending on-surface synthesis from 2D to 3D by cycloaddition with C60",

abstract = "As an efficient molecular engineering approach, on-surface synthesis (OSS) defines a special opportunity to investigate intermolecular coupling at the sub-molecular level and has delivered many appealing polymers. So far, all OSS is based on the lateral covalent bonding of molecular precursors within a single molecular layer; extending OSS from two to three dimensions is yet to be realized. Herein, we address this challenge by cycloaddition between C60 and an aromatic compound. The C60 layer is assembled on the well-defined molecular network, allowing appropriate molecular orbital hybridization. Upon thermal activation, covalent coupling perpendicular to the surface via [4 + 2] cycloaddition between C60 and the phenyl ring of the molecule is realized; the resultant adduct shows frozen orientation and distinct sub-molecular feature at room temperature and further enables lateral covalent bonding via [2 + 2] cycloaddition. This work unlocks an unconventional route for bottom-up precise synthesis of three-dimensional covalently-bonded organic architectures/devices on surfaces.",

author = "Pengcheng Ding and Shaoshan Wang and Cristina Mattioli and Zhuo Li and Guoqiang Shi and Ye Sun and Andr{\'e} Gourdon and Lev Kantorovich and Flemming Besenbacher and Federico Rosei and Miao Yu",

note = "Funding Information: This work is financially supported by the National Natural Science Foundation of China (21473045, M.Y.; 51772066, Y.S.; 52073074, Y.S.; 22272041, M.Y.), and State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology (2021TS08). F.R. is grateful to the Canada Research Chairs program for partial salary support. Publisher Copyright: {\textcopyright} 2023, Springer Nature Limited.",

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AU - Shi, Guoqiang

AU - Sun, Ye

AU - Gourdon, André

AU - Kantorovich, Lev

AU - Besenbacher, Flemming

AU - Rosei, Federico

AU - Yu, Miao

N1 - Funding Information: This work is financially supported by the National Natural Science Foundation of China (21473045, M.Y.; 51772066, Y.S.; 52073074, Y.S.; 22272041, M.Y.), and State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology (2021TS08). F.R. is grateful to the Canada Research Chairs program for partial salary support. Publisher Copyright: © 2023, Springer Nature Limited.

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Extending on-surface synthesis from 2D to 3D by cycloaddition with C₆₀

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