Surface-Confined Macrocyclization via Dynamic Covalent Chemistry

被引：9

作者：

Fu, Chaoying ^{[1
,2
,5
,6
]}

Miksatko, Jiri ^{[7
]}

Assies, Lea ^{[7
]}

Vrkoslav, Vladimir ^{[8
]}

Orlandi, Silvia ^{[3
]}

Kalbac, Martin ^{[7
]}

Kovaricek, Petr ^{[7
]}

Zeng, Xiaobin ^{[1
,2
]}

Zhou, Boping ^{[1
,2
]}

Muccioli, Luca ^{[3
,4
]}

Perepichka, Dmitrii F. ^{[5
]}

Orgiu, Emanuele ^{[6
]}

机构：

[1] Jinan Univ, Shenzhen Peoples Hosp, Clin Med Coll 2, Ctr Lab,Longhua Branch, Shenzhen 518120, Guangdong, Peoples R China

[2] Jinan Univ, Shenzhen PeoplesH osp, Clin Med Coll 2, Dept Infect Dis, Shenzhen 518120, Guangdong, Peoples R China

[3] Univ Bologna, Dipartimento Chim Ind Toso Montanan, I-40136 Bologna, Italy

[4] Univ Bordeaux, Inst Sci Mol, UMR 5255, F-33405 Talence, France

[5] McGill Univ, Dept Chem, Montreal, PQ H3A 0B8, Canada

[6] Energie Mat Telecommun Ctr, INRS, Varennes, PQ J3X 1S2, Canada

[7] Czech Acad Sci, J Heyrovsky Inst Phys Chem, Prague 18223, Czech Republic

[8] Czech Acad Sci, Inst Organ Chem & Biochem, Prague 16610, Czech Republic

来源：

ACS NANO | 2020年 / 14卷 / 03期

基金：

加拿大自然科学与工程研究理事会; 中国国家自然科学基金;

关键词：

dynamic covalent chemistry; on-surface synthesis; macrocycle; scanning tunneling microscopy; density functional theory; molecular dynamics simulation; HIGH-DILUTION SYNTHESIS; SUPPORTED SYNTHESIS; SINGLE; POLYMERIZATION; CONDENSATION; GRAPHITE; DRIVEN; 2D;

D O I：

10.1021/acsnano.9b07671

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Surface-confined synthesis is a promising approach to build complex molecular nanostructures including macrocycles. However, despite the recent advances in on-surface macro- cyclization under ultrahigh vacuum, selective synthesis of monodisperse and multicomponent macrocycles remains a challenge. Here, we report on an on-surface formation of [6 + 6] Schiff-base macrocycles via dynamic covalent chemistry. The macrocycles form two-dimensional crystalline domains on the micrometer scale, enabled by dynamic conversion of open-chain oligomers into well-defined similar to 3.0 nm hexagonal macrocycles. We further show that by tailoring the length of the alkyl substituents, it is possible to control which of three possible products-oligomers, macrocycles, or polymers-will form at the surface. In situ scanning tunneling microscopy imaging combined with density functional theory calculations and molecular dynamics simulations unravel the synergistic effect of surface confinement and solvent in leading to preferential on-surface macrocyclization.

引用

页码：2956 / 2965

页数：10

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