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One‐Step Simultaneous Synthesis of Circularly Polarized Luminescent Multiple Helicenes Using a Chrysene Framework
Author(s) -
Ikai Tomoyuki,
Yamakawa Shoya,
Suzuki Nozomu,
Yashima Eiji
Publication year - 2021
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.202100035
Subject(s) - helicene , chrysene , enantiomer , diastereomer , chirality (physics) , circular dichroism , chemistry , stereochemistry , aryl , intramolecular force , crystallography , photochemistry , organic chemistry , physics , molecule , symmetry breaking , quantum mechanics , nambu–jona lasinio model , chiral symmetry breaking , alkyl , anthracene
A series of multiple helicenes was simultaneously synthesized in one step by intramolecular cyclization of a single chrysene derivative containing two 2‐[(4‐alkoxyphenyl)ethynyl]phenyl units accompanied by rearrangements of the aryl pendants. The electrophile‐induced double cyclization with or without aryl migrations proceeded efficiently under acidic conditions to afford annulative π‐extension of the chrysene units and produced quadruple (QH‐ 2 ), triple (TH‐ 2 ), and double (DH‐ 2 ) helicenes containing [4]‐ and/or [5]helicene frameworks with dynamic and/or static helicene chirality in one step. Three multiple helicenes’ structures were determined by X‐ray crystallography and/or density functional theory calculations. The multiple TH‐ 2 and DH‐ 2 helicenes were separated into enantiomers because of the stable one and two [5]helicene moieties, respectively, and showed intense circular dichroism and circularly polarized luminescence. Although QH‐ 2 , which comprises four [4]helicene subunits, was not resolved into enantiomers, the TH‐ 2 enantiomers were further separated into a pair of diastereomers at low temperature resulting from their substituted [4]helicene chirality.