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On‐Surface Synthesis of Giant Conjugated Macrocycles
Author(s) -
Fan Cunrui,
Sun Bangjin,
Li Zhanbo,
Shi Jiwei,
Lin Tao,
Fan Jian,
Shi Ziliang
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202104090
Subject(s) - conjugated system , covalent bond , scanning tunneling microscope , chemistry , density functional theory , materials science , polymer chemistry , nanotechnology , polymer , organic chemistry , computational chemistry
We have achieved an on‐surface synthesis of giant conjugated macrocycles having a diameter of ≈7 nm and consisting of up to 30 subunits. The synthesis started with a debrominative coupling of the molecular precursors on a hot Ag(111) surface, leading to the formation of arched oligomeric chains and macrocycles. These products were revealed by scanning tunneling microscopy in combination with density functional theory to be covalent oligomers. These intermediates also display C–Ag organometallic bonds between parallel molecular subunits due to site‐selective debromination and the asymmetric molecular conformation. Subsequent cyclodehydrogenation at higher temperatures steered the final conjugation of the macrocycles. Our findings provide a novel design strategy toward π‐conjugated macrocycles and open up new opportunities for the precise synthesis of organic nanostructures.