NMR and crystallographic studies of a p-sulfonatocalix(4)arene-guest complex

Journal Article · Wed Dec 05 00:00:00 EST 1990 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00181a004· OSTI ID:5906517

Shinkai, Seiji; Araki, Koji; Matsuda, Tsutomu; Nishiyama, Nobuaki; Ikeda, Hirotaka ^[1]; Takasu, Isao; Iwamoto, Masakazu ^[2]

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1. Kyushu Univ., Fukuoka (Japan)
2. Miyazaki Univ. (Japan)

The {sup 1}H and {sup 13}C NMR spectra of a complex formed from tetrasodium p-sulfonatocalix(4)arene (1{sub 4}) and trimethylanilinium chloride (2) in D{sub 2}O showed that 2 is bound to the cavity of cone-shaped 1{sub 4}: in the acidic pH region (pD 0.4) the phenyl moiety resides in the cavity, whereas in the neutral pH region (pD 7.3) both the trimethylammonium and the phenyl moiety are included nonspecifically in the cavity. The difference was accounted for by the change in the electron density in the benzene {pi}-systems induced by the dissociation of OH groups. The complex was crystallized from acidic aqueous solution. The solid-state {sup 13}C NMR (CP-MAS) supports the inclusion of the phenyl moiety in the cavity. The X-ray crystallographic studies established that (1) 1{sub 4} adopts a cone conformation, (2) 1{sub 4} and 2 form a host-guest-type complex with the phenyl moiety inserted into the cavity, (3) not only the hydrophobic force but also the electrostatic force operates for guest inclusion, and (4) the overall structure is similar to that of clays, 1{sub 4} molecules being arranged into bilayers. These findings serve as a useful cross-link between solution complexes and solid-state complexes.

• OSTI ID: 5906517
• Journal Information: Journal of the American Chemical Society; (United States), Vol. 112:25; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
SULFUR COMPLEXES
MOLECULAR STRUCTURE
AMINES
AQUEOUS SOLUTIONS
BOND ANGLE
BOND LENGTHS
CATIONS
CHEMICAL SHIFT
HEAVY WATER
NUCLEAR MAGNETIC RESONANCE
X-RAY DIFFRACTION
CHARGED PARTICLES
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
DIMENSIONS
DISPERSIONS
HYDROGEN COMPOUNDS
IONS
LENGTH
MAGNETIC RESONANCE
MIXTURES
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
RESONANCE
SCATTERING
SOLUTIONS
WATER
360602* - Other Materials- Structure & Phase Studies