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NMR Study of Dynamics and Evolution of Guest Molecules in Kaolinite/Dimethyl Sulfoxide Intercalation Compound

Published online by Cambridge University Press:  28 February 2024

Shigenobu Hayashi
Shigenobu Hayashi*
Affiliation:
National Institute of Materials and Chemical Research, 1-1 Higashi, Tsukuba, Ibaraki 305, Japan
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Abstract

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Motion of the guest molecules in kaolinite/dimethyl sulfoxide (DMSO) intercalation compounds Al2Si2O5(OH)4∙(CH3)2SO has been studied by means of solid-state nuclear magnetic resonance (NMR) in the temperature range between 300 and 380 K, which is just below the evolution temperature. The 13C magic angle spinning (MAS) NMR spectra show 2 inequivalent methyl carbons: 1 methyl carbon is keyed in the ditrigonal hole of the silicate sheet, while the other is located parallel to the sheet. Above 320 K, the 2 peaks have different intensities, suggesting that the keyed methyl groups from some of the DMSO molecules are released from the hole. The 2H NMR spectra have been measured for kaolinite/DMSO-d6 intercalate. The methyl group of the interlayer DMSO molecule undergoes free rotation around its C3 axis over the temperature range studied. The axis of rotation is fixed at the low temperature (about 160 K), and the methyl group initiates a wobbling motion whose amplitude increases with temperature. The wobbling angles have an anisotropy, estimated from theoretical analysis of the 2H spectral line shapes. The DMSO molecules released from the silicate layer undergo anisotropic rotation of the whole molecule.

Keywords

2H NMR13C NMRDimethyl SulfoxideIntercalation CompoundKaoliniteLayered Silicate
Type
Research Article
Information
Clays and Clay Minerals , Volume 45 , Issue 5 , October 1997 , pp. 724 - 732
Copyright
Copyright © 1997, The Clay Minerals Society

References

Adams, J.M., 1983 Hydrogen atom positions in kaolinite by neutron profile refinement Clays Clay Miner 31 352–356 10.1346/CCMN.1983.0310504.CrossRefGoogle Scholar
Barnes, R.G., 1974 Deuteron quadrupole coupling tensors in solids Adv Nuc Quadrupole Reson 1 335–355.Google Scholar
Bish, D.L., 1993 Rietveld refinement of the kaolinite structure at 1.5 K Clays Clay Miner 41 738–744 10.1346/CCMN.1993.0410613.CrossRefGoogle Scholar
Bish, D.L. and Von Dreele, R.B., 1989 Rietveld refinement of nonhydrogen atomic positions in kaolinite Clays Clay Miner 37 289–296 10.1346/CCMN.1989.0370401.CrossRefGoogle Scholar
Costanzo, P.M. and Giese, R.F. Jr., 1990 Ordered and disordered organic intercalates of 8.4-Å, synthetically hydrated kaolinite Clays Clay Miner 38 160–170 10.1346/CCMN.1990.0380207.CrossRefGoogle Scholar
Duer, M.J. and Rocha, J., 1992 A two-dimensional solid-state 2H exchange NMR study of the molecular motion in the kaolinite:DMSO intercalation compound J Magn Reson 98 524–533.Google Scholar
Duer, M.J. Rocha, J. and Klinowski, J., 1992 Solid-state NMR studies of the molecular motion in the kaolinite:DMSO intercalate J Am Chem Soc 114 6867–6874 10.1021/ja00043a036.CrossRefGoogle Scholar
Hayashi, S., 1995 NMR study of dynamics of dimethyl sulfoxide molecules in kaolinite/dimethyl sulfoxide intercalation compound J Phys Chem 99 7120–7129 10.1021/j100018a053.CrossRefGoogle Scholar
Hayashi, S. and Akiba, E., 1994 Interatomic distances in layered silicates and their intercalation compounds as studied by cross polarization NMR Chem Phys Lett 226 495–500 10.1016/0009-2614(94)00773-X.CrossRefGoogle Scholar
Olejnik, S. Aylmore, L.A.G. Posner, A.M. and Quirk, J.P., 1968 Infrared spectra of kaolin mineral-dimethyl sulfoxide complexes J Phys Chem 72 241–249 10.1021/j100847a045.CrossRefGoogle Scholar
Olejnik, S. Posner, A.M. and Quirk, J.P., 1970 The intercalation of polar organic compounds into kaolinite Clay Miner 8 421–434 10.1180/claymin.1970.008.4.05.CrossRefGoogle Scholar
Raupach, M. Barron, P.F. and Thompson, J.G., 1987 Nuclear magnetic resonance, infrared, and X-ray powder diffraction study of dimethylsulfoxide and dimethylselenoxide intercalates with kaolinite Clays Clay Miner 35 208–219 10.1346/CCMN.1987.0350307.CrossRefGoogle Scholar
Thompson, J.G., 1985 Interpretation of solid state 13C and 29Si nuclear magnetic resonance spectra of kaolinite intercalates Clays Clay Miner 33 173–180 10.1346/CCMN.1985.0330302.CrossRefGoogle Scholar
Thompson, J.G. and Cuff, C., 1985 Crystal structure of kaolinite: dimethylsulfoxide intercalate Clays Clay Miner 33 490–500 10.1346/CCMN.1985.0330603.CrossRefGoogle Scholar
Young, R.A. and Hewat, A.W., 1988 Verification of the triclinic crystal structure of kaolinite Clays Clay Miner 36 225–232 10.1346/CCMN.1988.0360303.CrossRefGoogle Scholar