Azabuckybowl-Based Molecular Tweezers as C60 and C70 Receptors

Motoki Takeda, Satoru Hiroto, Hiroki Yokoi, Sangsu Lee, Dongho Kim, Hiroshi Shinokubo

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

We designed and synthesized molecular tweezers consisting of nitrogen-embedded buckybowl subunits. The judicious choice of the covalent linkers modulated their binding strength with C60 or C70 in solution. Titration studies by optical and 1H NMR analyses revealed a 1:1 composition of the resulting complexes. X-ray diffraction analysis elucidated their solid-state structures, in which two azabuckybowl units surround one fullerene molecule. The large association constants stabilize the complexes toward redox reactions and the purification process on silica-gel column chromatography. The linker enabled tuning of the cavity size for binding of fullerenes, achieving complementary fullerene hosts for C60 and C70: the carbazole-bridged dimer preferentially associates with C70 over C60, while the phenanthrene-bridged dimer interacts with C60 more strongly than C70. Electrochemical analysis in combination with density functional theory calculations indicated the existence of intermolecular charge-transfer interactions between the buckybowl units and the fullerenes. Nonlinear optical measurements showed that the two-photon absorption cross sections of the molecular tweezers are enhanced upon association with fullerenes.

Original languageEnglish
Pages (from-to)6336-6342
Number of pages7
JournalJournal of the American Chemical Society
Volume140
Issue number20
DOIs
Publication statusPublished - 2018 May 23

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Fullerenes
Dimers
Association reactions
Silica Gel
Photons
Column chromatography
X-Ray Diffraction
Redox reactions
Oxidation-Reduction
Gel Chromatography
Silica gel
Titration
Nitrogen
X ray diffraction analysis
Purification
Density functional theory
Charge transfer
Tuning
Nuclear magnetic resonance
Molecules

All Science Journal Classification (ASJC) codes

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

Cite this

Takeda, Motoki ; Hiroto, Satoru ; Yokoi, Hiroki ; Lee, Sangsu ; Kim, Dongho ; Shinokubo, Hiroshi. / Azabuckybowl-Based Molecular Tweezers as C60 and C70 Receptors. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 20. pp. 6336-6342.
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Takeda, M, Hiroto, S, Yokoi, H, Lee, S, Kim, D & Shinokubo, H 2018, 'Azabuckybowl-Based Molecular Tweezers as C60 and C70 Receptors', Journal of the American Chemical Society, vol. 140, no. 20, pp. 6336-6342. https://doi.org/10.1021/jacs.8b02327

Azabuckybowl-Based Molecular Tweezers as C60 and C70 Receptors. / Takeda, Motoki; Hiroto, Satoru; Yokoi, Hiroki; Lee, Sangsu; Kim, Dongho; Shinokubo, Hiroshi.

In: Journal of the American Chemical Society, Vol. 140, No. 20, 23.05.2018, p. 6336-6342.

Research output: Contribution to journalArticle

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AU - Shinokubo, Hiroshi

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