Olefin cyclization on Cu(111) driven by subsurface carbon and ultraviolet irradiation

Zhuo Li; Guoqiang Shi; Junfeng Zhou; Yanghan Chen; Pengcheng Ding; Wei Yi; Ye Sun; Xin Yang; Lev N. Kantorovich; Federico Rosei; Miao Yu

doi:10.1016/j.xcrp.2022.101172

Olefin cyclization on Cu(111) driven by subsurface carbon and ultraviolet irradiation

Zhuo Li, Guoqiang Shi, Junfeng Zhou, Yanghan Chen, Pengcheng Ding, Wei Yi, Ye Sun, Xin Yang, Lev N. Kantorovich, Federico Rosei, Miao Yu^*

^*Corresponding author for this work

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

Abstract

Among several major unresolved challenges in reaction chemistry, controlling the yield and selectivity is particularly crucial. For on-surface synthesis (OSS), a prototype for basic understanding of reaction mechanisms, such control remains elusive. Here, using olefin cyclization, an important reaction in organic synthesis yet unknown for OSS to the best of our knowledge, as the model system, we propose a strategy to address this challenge by introducing carbon into the subsurface of Cu(111) (C-Cu^δ+) and UV irradiation. The total olefin coupling rate on C-Cu^δ+ increases to 10.1- and 5.3-fold higher than that on pristine Cu(111) at 298 and 323 K, respectively. The initial cyclization temperature reduces by 55 K on C-Cu^δ+. UV irradiation further promotes the cyclization ratio from 22% to 40.3%. By integrating surface catalysis of the substrate with photochemistry of light-absorbing reactants, our results may open up a promising route for overcoming high reaction barriers and regulating selectivity in OSS.

Original language	English
Article number	101172
Journal	Cell Reports Physical Science
Volume	3
Issue number	12
DOIs	https://doi.org/10.1016/j.xcrp.2022.101172
Publication status	Published - 21 Dec 2022

Keywords

olefin cyclization
on-surface synthesis
photochemistry
subsurface doping
surface catalysis

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10.1016/j.xcrp.2022.101172

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title = "Olefin cyclization on Cu(111) driven by subsurface carbon and ultraviolet irradiation",

abstract = "Among several major unresolved challenges in reaction chemistry, controlling the yield and selectivity is particularly crucial. For on-surface synthesis (OSS), a prototype for basic understanding of reaction mechanisms, such control remains elusive. Here, using olefin cyclization, an important reaction in organic synthesis yet unknown for OSS to the best of our knowledge, as the model system, we propose a strategy to address this challenge by introducing carbon into the subsurface of Cu(111) (C-Cuδ+) and UV irradiation. The total olefin coupling rate on C-Cuδ+ increases to 10.1- and 5.3-fold higher than that on pristine Cu(111) at 298 and 323 K, respectively. The initial cyclization temperature reduces by 55 K on C-Cuδ+. UV irradiation further promotes the cyclization ratio from 22% to 40.3%. By integrating surface catalysis of the substrate with photochemistry of light-absorbing reactants, our results may open up a promising route for overcoming high reaction barriers and regulating selectivity in OSS.",

keywords = "olefin cyclization, on-surface synthesis, photochemistry, subsurface doping, surface catalysis",

author = "Zhuo Li and Guoqiang Shi and Junfeng Zhou and Yanghan Chen and Pengcheng Ding and Wei Yi and Ye Sun and Xin Yang and Kantorovich, {Lev N.} and Federico Rosei and Miao Yu",

note = "Funding Information: This work is financially supported by the National Natural Science Foundation of China ( 21473045 , 51772066 , and 52073074 ) and the 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} 2022 The Authors",

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day = "21",

doi = "10.1016/j.xcrp.2022.101172",

language = "English",

volume = "3",

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TY - JOUR

T1 - Olefin cyclization on Cu(111) driven by subsurface carbon and ultraviolet irradiation

AU - Li, Zhuo

AU - Shi, Guoqiang

AU - Zhou, Junfeng

AU - Chen, Yanghan

AU - Ding, Pengcheng

AU - Yi, Wei

AU - Sun, Ye

AU - Yang, Xin

AU - Kantorovich, Lev N.

AU - Rosei, Federico

AU - Yu, Miao

N1 - Funding Information: This work is financially supported by the National Natural Science Foundation of China ( 21473045 , 51772066 , and 52073074 ) and the 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: © 2022 The Authors

PY - 2022/12/21

Y1 - 2022/12/21

N2 - Among several major unresolved challenges in reaction chemistry, controlling the yield and selectivity is particularly crucial. For on-surface synthesis (OSS), a prototype for basic understanding of reaction mechanisms, such control remains elusive. Here, using olefin cyclization, an important reaction in organic synthesis yet unknown for OSS to the best of our knowledge, as the model system, we propose a strategy to address this challenge by introducing carbon into the subsurface of Cu(111) (C-Cuδ+) and UV irradiation. The total olefin coupling rate on C-Cuδ+ increases to 10.1- and 5.3-fold higher than that on pristine Cu(111) at 298 and 323 K, respectively. The initial cyclization temperature reduces by 55 K on C-Cuδ+. UV irradiation further promotes the cyclization ratio from 22% to 40.3%. By integrating surface catalysis of the substrate with photochemistry of light-absorbing reactants, our results may open up a promising route for overcoming high reaction barriers and regulating selectivity in OSS.

AB - Among several major unresolved challenges in reaction chemistry, controlling the yield and selectivity is particularly crucial. For on-surface synthesis (OSS), a prototype for basic understanding of reaction mechanisms, such control remains elusive. Here, using olefin cyclization, an important reaction in organic synthesis yet unknown for OSS to the best of our knowledge, as the model system, we propose a strategy to address this challenge by introducing carbon into the subsurface of Cu(111) (C-Cuδ+) and UV irradiation. The total olefin coupling rate on C-Cuδ+ increases to 10.1- and 5.3-fold higher than that on pristine Cu(111) at 298 and 323 K, respectively. The initial cyclization temperature reduces by 55 K on C-Cuδ+. UV irradiation further promotes the cyclization ratio from 22% to 40.3%. By integrating surface catalysis of the substrate with photochemistry of light-absorbing reactants, our results may open up a promising route for overcoming high reaction barriers and regulating selectivity in OSS.

KW - olefin cyclization

KW - on-surface synthesis

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Olefin cyclization on Cu(111) driven by subsurface carbon and ultraviolet irradiation

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