Conjugated double helices <i>via</i> self-dimerization of α,α′-dianilinotripyrrins

• 梅谷, 将隆

  Department of Chemistry, Graduate School of Science, Kyoto University

• 田中, 隆行

  Department of Chemistry, Graduate School of Science, Kyoto University

• 大須賀, 篤弘

  Department of Chemistry, Graduate School of Science, Kyoto University

書誌事項

タイトル別名

• Conjugated double helices via self-dimerization of α,α′-dianilinotripyrrins

抄録

A new motif for artificial double helices was developed on the basis of α, α′-disubstituted tripyrrin. α, α′-Dibromotripyrrin 3 was prepared by gentle bromination at the pyrrolic α-positions of 5, 10-diphenyltripyrrane followed by oxidation with DDQ. Nucleophilic substitution reactions of 3 with anilines proceeded efficiently to furnish a series of α, α′-dianilinotripyrrins 4–11, which displayed monomeric and dimeric forms depending upon the solvent used for crystallization and the structures of the substituted anilines. Dimeric forms show double helical structures with smooth π-conjugation as indicated by their absorption spectra. van't-Hoff plot analyses revealed that the dimerizations in CDCl3 are enthalpy-driven. Larger association constants of the dimerization are attained for 3, 5-di-t-butylanilino- and 3, 5-bis(trifluoromethyl)anilino-substituted tripyrrins (7 and 8) via additional multiple intermolecular interactions. In a nonpolar and aprotic solvent, tripyrrins (9 and 10) bearing bulkier 1-naphthylamino and mesitylamino groups do not dimerize but undergo unique tautomerization.

収録刊行物

• Chemical Science

  Chemical Science 9 6853-6859, 2018-01-01

  Royal Society of Chemistry

キーワード

• General Chemistry

詳細情報

• CRID: 1050564288161175424
• NII論文ID: 120006534587
• ISSN: 20416520
• ISSN: 20416539
• DOI: 10.1039/c8sc02739k
• HANDLE: 2433/234933
• Web Site: http://pubs.rsc.org/en/content/articlepdf/2018/SC/C8SC02739K
• 本文言語コード: en
• 資料種別: journal article
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