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Synthesis, Structures, and Properties of Highly Strained Cyclophenylene–Ethynylenes with Axial and Helical Chirality
Author(s) -
Wang LiHsiang,
Hayase Norihiko,
Sugiyama Haruki,
Nogami Juntaro,
Uekusa Hidehiro,
Tanaka Ken
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202006959
Subject(s) - homo/lumo , biphenyl , chirality (physics) , axial chirality , dihedral angle , crystallography , materials science , chemistry , computational chemistry , stereochemistry , enantioselective synthesis , molecule , organic chemistry , physics , catalysis , nambu–jona lasinio model , quark , hydrogen bond , chiral symmetry breaking , quantum mechanics
Single and double cyclophenylene–ethynylenes (CPEs) with axial and helical chirality have been synthesized by the Sonogashira cross‐coupling of di‐ and tetraethynyl biphenyls with a U‐shaped prearomatic diiodoparaphenylene followed by reductive aromatization. X‐ray crystallographic analyses and DFT calculations revealed that the CPEs possess highly twisted bent structures. Bend angles on the edge of the paraphenylene units were close to the value of [5]cycloparaphenylene (CPP)—the smallest CPP to date. The double and single CPEs possessed stable chirality despite flexible biphenyl structures because of the high strain in the diethynyl–paraphenylene moiety. In both the single and double CPEs, orbital interactions along the biphenyl axis were observed by DFT calculations in LUMO and LUMO+2 of the single CPE and LUMO+1 of the double CPE, which likely cause lowering of these orbital energies. Concerning chiroptical properties: boosting of the g abs value was observed in the biphenyl‐based double CPE, as well as the binaphthyl‐based single CPE, compared to the biphenyl‐based single CPE.