Synthesis, Structures, and Properties of Highly Strained Cyclophenylene–Ethynylenes with Axial and Helical Chirality

Li Hsiang Wang, Norihiko Hayase, Haruki Sugiyama, Juntaro Nogami, Hidehiro Uekusa, Ken Tanaka

研究成果: Article査読

抄録

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 gabs value was observed in the biphenyl-based double CPE, as well as the binaphthyl-based single CPE, compared to the biphenyl-based single CPE.

本文言語English
ページ(範囲)17951-17957
ページ数7
ジャーナルAngewandte Chemie - International Edition
59
41
DOI
出版ステータスPublished - 2020 10 5

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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