Porphyrin Arch-Tapes: Synthesis, Contorted Structures, and Full Conjugation

Norihito Fukui, Taeyeon Kim, Dongho Kim, Atsuhiro Osuka

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Porphyrin tapes possessing meso-meso β-β β-β triple direct linkages have been targets of extensive studies because of their fully conjugated characteristic π-electronic networks. In this paper, we report porphyrin arch-tapes that bear additional carbonyl group(s) or methylene group(s) inserted between one of the β-β linkage(s) of the porphyrin tapes. The carbonyl-inserted porphyrin arch-tapes were efficiently synthesized by double fusion reactions of β-to-β carbonyl-bridged porphyrin oligomers with DDQ and Sc(OTf)3, and were converted to the methylene-bridged porphyrin arch-tapes via Luche reduction with NaBH4 and CeCl3 followed by ionic hydrogenation with HBF4·OEt2 and BH3·NEt3. While the conventional porphyrin tapes display rigid and planar structures and low solubilities, these porphyrin arch-tapes show remarkably contorted structures, flexible conformations, and improved solubilities because of the presence of the incorporated seven-membered ring(s). Interestingly, the methylene-inserted arch-tapes exhibited conjugative electronic interactions that were comparable to those of porphyrin tapes probably owing to through-space interaction in the contorted conformations. The carbonyl-inserted arch-tapes displayed distinctly larger conjugative interactions owing to an active involvement of the carbonyl group(s) in the electronic conjugation. A similar trend was observed in the nonlinear optical properties, as evidenced by their two-photon absorption cross sections. Furthermore, as a benefit of the contorted structures, these porphyrin arch-tapes can catch C60 fullerene effectively. Naturally, the electron-rich methylene-bridged arch-tapes exhibited larger association constants than the electron-deficient carbonyl-bridged arch-tapes. Among these arch-tapes, a methylene-bridged syn-Ni(II) porphyrin trimer recorded the largest association constant of (1.5 ± 0.4) × 107 M-1 in toluene at 25 °C.

Original languageEnglish
Pages (from-to)9075-9088
Number of pages14
JournalJournal of the American Chemical Society
Issue number26
Publication statusPublished - 2017 Jul 5

Bibliographical note

Funding Information:
The work at Kyoto University was supported by Grants-in-Aid from JSPS (Nos.: 25220802 (Scientific Research (S)), 16K13952 (Exploratory Research)). N.F. acknowledges a JSPS Fellowship for Young Scientists. This work at Yonsei University was supported by the Global Research Laboratory Program (2013K1A1A2A02050183) funded by the Ministry of Science, ICT & Future, Korea (D.K.).

Publisher Copyright:
© 2017 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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