The effect of a highly twisted CC double bond on the electronic structures of 9,9′-bifluorenylidene derivatives in the ground and excited states

Atsuro Takai, Dylan J. Freas, Toshikane Suzuki, Manabu Sugimoto, Jan Labuta, Rie Haruki, Reiji Kumai, Shin Ichi Adachi, Hayato Sakai, Taku Hasobe, Yoshitaka Matsushita, Masayuki Takeuchi

研究成果: Article査読

13 被引用数 (Scopus)

抄録

We synthesized methyl-substituted 9,9′-bifluorenylidene (9,9′-BF) derivatives in which two planar fluorene units are connected through a CC double bond. The CC double bond is twisted owing to the steric crowding between the fluorene units, and by introducing substituents at 1,1′-positions (inner space of 9,9′-BF) it becomes more twisted. Indeed, single crystal X-ray structural analysis and theoretical calculation reveal that the dihedral angle between two fluorene π-planes of a 1,1′-dimethyl-substituted 9,9′-BF is 56°, which is clearly larger than those of pristine 9,9′-BF (42°) and 1-methyl-substituted 9,9′-BF (50°). The twisted conformation of 1,1′-dimethyl-substituted 9,9′-BF facilitates the cis-trans isomerization process which we assessed quantitatively by variable-temperature NMR measurements. The 9,9′-BF derivatives with different numbers of methyl groups also exhibit remarkable changes in optoelectronic properties, primarily because of the change in the twisting angle of the central CC double bond. Theoretical calculation further indicates that the electronic structures of methyl-substituted 9,9′-BF derivatives in the excited states are considerably different from those of pristine 9,9′-BF.

本文言語English
ページ(範囲)650-657
ページ数8
ジャーナルOrganic Chemistry Frontiers
4
5
DOI
出版ステータスPublished - 2017 5

ASJC Scopus subject areas

  • 有機化学

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