Premium
Stereoselective On‐Surface Cyclodehydrofluorization of a Tetraphenylporphyrin and Homochiral Self‐Assembly
Author(s) -
Chen Hui,
Tao Lei,
Wang Dongfei,
Wu ZhuoYan,
Zhang JunLong,
Gao Song,
Xiao Wende,
Du Shixuan,
Ernst KarlHeinz,
Gao HongJun
Publication year - 2020
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.202005425
Subject(s) - stereoselectivity , steric effects , cooperativity , intermolecular force , selectivity , porphyrin , tetraphenylporphyrin , chemistry , scanning tunneling microscope , density functional theory , crystallography , stereochemistry , catalysis , photochemistry , materials science , computational chemistry , molecule , nanotechnology , organic chemistry , biochemistry
The thermally induced cyclodehydrofluorization of iron tetrakis(pentafluorophenyl)porphyrin proceeded highly stereoselectively to give a prochiral product on a gold surface in an ultrahigh vacuum, whereas dehydrocyclization of the respective iron tetrakisphenylporphyrin did not show such selectivity. Stereoselectivity was predominantly observed for closely packed layers, which is an indication of intermolecular cooperativity and steric constraints induced by adjacent species. Density functional theory identified intermolecular packing constraints as the origin of such selectivity during the reaction. Scanning tunneling microscopy revealed the formation of an enantiomerically pure two‐dimensional self‐assembly as a conglomerate of mirror domains. On‐surface two‐dimensional topochemistry, as reported herein, may open new routes for stereoselective synthesis.