Self-assembled, helically stacked anionic aggregates of 2,5,8,11-tetra-tert-butylcycloocta[1,2,3,4-def; 5,6,7,8-d′e′f′] bisbiphenylene, stabilized by electrostatic interactions

Roy Shenhar, Hua Wang, Roy E. Hoffman, Limor Frish, Liat Avram, Itamar Willner, Andrzej Rajca, Mordecai Rabinovitz

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

Tetraanions of alkyl-substituted derivatives of cycloocta[1,2,3,4-def, 5,6,7,8-d′e′f′]bisbiphenylene (BPD) and their counter lithium cations self-assemble to form helically stacked assemblies, including a dimer, a trimer, and a tetramer. NMR self-diffusion measurements and unprecedented magnetic shielding effects for the sandwiched lithium cations support their aggregated nature. The D2-tetramer assembly is fully characterized by NMR spectroscopy, providing unequivocal evidence for a helix of four tetraanionic BPD layers with an estimated relative twist angle of about 45° and interlayer spacing of ca. 4 Å. The barrier for racemization through the in-plane inter-deck rotation is ΔG200 = 9.5 ± 0.2 kcal mol-1 in the dimer compared to > 15 kcal mol-1in the tetramer.

Original languageEnglish (US)
Pages (from-to)4685-4692
Number of pages8
JournalJournal of the American Chemical Society
Volume124
Issue number17
DOIs
StatePublished - May 1 2002

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Coulomb interactions
Static Electricity
Lithium
Dimers
Cations
Positive ions
Magnetic shielding
Nuclear magnetic resonance spectroscopy
Magnetic Resonance Spectroscopy
Nuclear magnetic resonance
Derivatives

ASJC Scopus subject areas

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

Cite this

Self-assembled, helically stacked anionic aggregates of 2,5,8,11-tetra-tert-butylcycloocta[1,2,3,4-def; 5,6,7,8-d′e′f′] bisbiphenylene, stabilized by electrostatic interactions. / Shenhar, Roy; Wang, Hua; Hoffman, Roy E.; Frish, Limor; Avram, Liat; Willner, Itamar; Rajca, Andrzej; Rabinovitz, Mordecai.

In: Journal of the American Chemical Society, Vol. 124, No. 17, 01.05.2002, p. 4685-4692.

Research output: Contribution to journalArticle

Shenhar, Roy ; Wang, Hua ; Hoffman, Roy E. ; Frish, Limor ; Avram, Liat ; Willner, Itamar ; Rajca, Andrzej ; Rabinovitz, Mordecai. / Self-assembled, helically stacked anionic aggregates of 2,5,8,11-tetra-tert-butylcycloocta[1,2,3,4-def; 5,6,7,8-d′e′f′] bisbiphenylene, stabilized by electrostatic interactions. In: Journal of the American Chemical Society. 2002 ; Vol. 124, No. 17. pp. 4685-4692.
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abstract = "Tetraanions of alkyl-substituted derivatives of cycloocta[1,2,3,4-def, 5,6,7,8-d′e′f′]bisbiphenylene (BPD) and their counter lithium cations self-assemble to form helically stacked assemblies, including a dimer, a trimer, and a tetramer. NMR self-diffusion measurements and unprecedented magnetic shielding effects for the sandwiched lithium cations support their aggregated nature. The D2-tetramer assembly is fully characterized by NMR spectroscopy, providing unequivocal evidence for a helix of four tetraanionic BPD layers with an estimated relative twist angle of about 45° and interlayer spacing of ca. 4 {\AA}. The barrier for racemization through the in-plane inter-deck rotation is ΔG200‡ = 9.5 ± 0.2 kcal mol-1 in the dimer compared to > 15 kcal mol-1in the tetramer.",
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AU - Hoffman, Roy E.

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