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Towards the Highly Efficient Synthesis and Selective Methylation of C(sp 3 )‐Bridged [6]Cycloparaphenylenes from Fluoren[3]arenes
Author(s) -
Du XuSheng,
Zhang DaWei,
Guo Yan,
Li Jing,
Han Ying,
Chen ChuanFeng
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202102701
Subject(s) - demethylation , intramolecular force , chemistry , aryl , methylation , fluorescence , crystal structure , stereochemistry , crystallography , organic chemistry , dna , biochemistry , gene expression , alkyl , physics , quantum mechanics , dna methylation , gene
Abstract An approach to the highly efficient synthesis of C(sp3)‐bridged [6]cycloparaphenylenes ( C[6]CPPs ) from fluoren[3]arenes ( F[3]As ) was developed. Consequently, F[3]As as a new kind of macrocyclic arenes were synthesized. Followed by the demethylation, triflation and intramolecular aryl–aryl coupling reactions, C[6]CPPs were then conveniently obtained. Interestingly, C[6]CPPs could be selectively methylated to produce their fully outer‐methyl‐substituted derivatives. The crystal structures showed the hydroxyl‐substituted F[3]As had bowl‐shaped conformations, and the C[6]CPPs exhibited rigid belt‐shaped structures with deep cavities. Moreover, C[6]CPPs exhibited high HOMO energies and narrow energy gaps. An unclosed belt was further obtained, and it not only showed a similar narrow energy gap to those of the aromatic belts, but also displayed strong fluorescence property, which can play a vital role in the design and synthesis of new aromatic belts.