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

33 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

All Science Journal Classification (ASJC) codes

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

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