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Stereochemistry and Molecular Recognition on the Surface of a Smectite Clay Mineral

Published online by Cambridge University Press:  01 January 2024

Akihiko Yamagishi  and
Hisako Sato
Akihiko Yamagishi*
Affiliation:
Department of Chemistry, Faculty of Science, Toho University, Chiba 274-8510, Japan
Hisako Sato
Affiliation:
Department of Chemistry, Graduate School of Science and Engineering, Ehime University, 2-5 Bunkyo-cho, Matsuyama 790-8577, Japan
*
*E-mail address of corresponding author: akihiko.yamagishi@sci.toho-u.ac.jp
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Abstract

Attempts at optical resolution and asymmetric syntheses using smectite clay minerals are described. Use of the method was prompted by the discovery that the saturated adsorption of a tris(chelated) metal complex, [Ru(1,10-phenanthroline)3]2+, by Na-montmorillonite depended heavily on the stereochemical properties. The pure enantiomer was adsorbed by cation exchange at negative surface sites of the clay mineral, while the racemic mixture was adsorbed to two times excess of the cation exchange capacity. The chelate takes a uniform orientation on a clay mineral surface due to the matching between the molecular symmetry and the two-dimensional network of a phyllosilicate layer. On a clay mineral surface covered with the enantiomeric chelates, a vacant space capable of chiral discrimination was generated. Based on this, an ion-exchange adduct of smectite and the chiral chelate was used as an adsorbent for separating racemic mixtures or selectively producing either one of the optical isomers.

Keywords

Asymmetric SynthesesChiral SensingCircular DichroismClay-modified ElectrodesElectric DichroismLB FilmsMolecular ChiralityOptical ResolutionStereoselectivityTris (1,10-phenanthroline)metal(II)
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 4 , August 2012 , pp. 411 - 419
Copyright
Copyright © Clay Minerals Society 2012

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Footnotes

§

2012 Recipient of the Marilyn & Sturges W. Bailey Distinguished Member Award of The Clay Minerals Society (see p. 440)

References

Bondy, S.C. and Harrington, M., 1979 L-amino acids and Dglucose bind stereospecifically to a colloidal clay Science 203 1243–1244.CrossRefGoogle ScholarPubMed
Fujimoto, N. Mori, Y. Yamagishi, A. and Sato, H., 2010 Molecular recognition of star-burst tetranuclear Ru(III) complexes on a chirally modified clay surface Chemical Communications 46 5473–5474.CrossRefGoogle ScholarPubMed
Fujita, S. Sato, H. Kakegawa, N. and Yamagishi, A., 2006 Enantioselective photooxidation of a sulfide by a chiral ruthenium(II) complex immobilized on a montmorillonite clay surface Journal of Physical Chemistry B 110 2533–2540.CrossRefGoogle ScholarPubMed
He, J.X. Sato, H. Umemura, Y. and Yamagishi, A., 2005 Sensing of molecular chirality on an electrode modified with a clay-metal complex hybrid film Journal of Physical Chemistry B 109 4679–4683.Google Scholar
Inukai, K. Hotta, Y. Tomura, S. Takahashi, M. and Yamagishi, A., 2000 Preparation of the Langmuir-Blodgett film of a clay-alkylammonium adduct and its use as a barrier for interlayer photo-induced electron transfer Langmuir 16 7679–7684.CrossRefGoogle Scholar
Kameda, J. Yamagishi, A. and Kogure, T., 2005 Morphological characteristics of ordered kaolinite investigation using electron backscattered diffusion (EBSD) American Mineralogist 90 1462–1465.CrossRefGoogle Scholar
Kawasaki, T. Omine, T. Suzuki, K. Sato, H. Yamagishi, A. and Soai, K., 2009 Highly enantioselective asymmetric autocatalysis using chiral ruthenium complex-ion-exchanged synthetic saponite as chiral initiator Organic & Biomolecular Chemistry 7 1073–1075.CrossRefGoogle Scholar
Loeppert, R.H. Mortland, M.M. and Pinnavaia, T.J., 1979 Synthesis and properties of heat stable expanded smectite and vermiculite Clays and Clay Minerals 27 201–208.CrossRefGoogle Scholar
Nakamura, Y. Yamagishi, A. Matsumoto, A. Tohkubo, K. and Ohtsu, Y., 1988b High performance liquid column chromatography on a column of spherically shaped synthetic hectorite Journal of Chromatography 482 165–167.CrossRefGoogle Scholar
Nakamura, Y. Yamagishi, A. Iwamoto, T. and Koga, M., 1988b Adsorption properties of montmorillonite and synthetic saponite as packing materials in liquid column chromatography Clays and Clay Minerals 36 530–536.CrossRefGoogle Scholar
Sato, H. Yamagishi, A. and Kato, S., 1992 Monte Carlo simulations of the interactions of metal complexes with the silicate sheets of a clay Journal of the American Chemical Society 114 10933–10940.CrossRefGoogle Scholar
Sato, H. Yamagishi, A. and Kawamura, T., 2001 Molecular simulation for flexibility of a single clay layer Journal of Physical Chemistry B 105 7990–7997.CrossRefGoogle Scholar
Sato, H. Mori, Y. Fukuda, Y. and Yamagishi, A., 2009 Syntheses and vibrational circular dichroism spectra of the complete series of [Ru(-)- or (+)-tfac]n(acac)n] (n = 0 ~ 3, tfac = 3-trifluoroacetylcamphoraro and acac = acetyacetonato) Inorganic Chemistry 48 4353–4361.CrossRefGoogle Scholar
Sato, H. Tamura, K. Ohara, K. Nagaoka, S.-I. and Yamagishi, A., 2011a Hybridization of clay minerals with the floating film of a cationic Ir(III) complex at an air-water interface New Journal of Chemistry 35 394–399.CrossRefGoogle Scholar
Sato, H. Tamura, K. Aoki, R. Kato, M. and Yamagishi, A., 2011b Enantioselective sensing by luminescence from cyclometalated iridium(III) complexes adsorbed on a colloidal saponite Chemistry Letters 40 65–67.CrossRefGoogle Scholar
Sato, H. Sato, F. Taniguchi, M. and Yamagishi, A., 2012 Chirality effects on core-periphery connection in a star-burst type tetranuclear complex: Application of vibrational circular dichroism spectroscopy Dalton Transactions 41 1709–1712.CrossRefGoogle Scholar
Shimada, T. Yamada, H. and Umemura, Y., 2012 Surface potential studies on adsorption processes of a clay nanosheet onto a floating monolayer film of an amphiphilic ammonium cation Journal of Physical Chemistry B 116 4484–4491.CrossRefGoogle Scholar
Suzuki, Y. Matsunaga, R. Sato, H. Kogure, T. Akihiko, A. and Kawamata, J., 2009 Non-centrosymmetric behavior of a clay film ion-exchanged with chiral metal complexes Chemical Communications 45 6964–6966.CrossRefGoogle Scholar
Takahashi, S. Tanaka, R. Wakabayashi, N. Taniguchi, M. and Yamagishi, A., 2003 Design of a chiral surface by modifying an anionically charged single-layered inorganic compound with metal complexes Langmuir 19 6122–6125.CrossRefGoogle Scholar
Tamura, K. Setstuda, H. Taniguchi, M. and Yamagishi, A., 1999 Application of the Langmuir-Blodgett technique to prepare a clay-metal complex hybrid film Langmuir 15 6915–6920.CrossRefGoogle Scholar
Taniguchi, M. Kaneyoshi, M. Nakamura, Y. Yamagishi, A. and Iwamoto, T., 1990 A stopped-flow electric dichroism study on adsorption of metal chelates by a colloidal clay Journal Physical Chemistry 94 5896–5900.CrossRefGoogle Scholar
Taniguchi, M. Yamagishi, A. and Iwamoto, T., 1991 X-ray diffraction and electric dichroism studies on the adsorption of metal complexes by a clay Journal of Physical Chemistry 30 2462–2467.Google Scholar
Umemura, Y. and Shinohara, E., 2004 Two-dimensional molecular ordering of Os(II) complexes in organo-clay hybrid ultrathin film Chemical Communications 42 1110–1111.CrossRefGoogle Scholar
Umemura, Y. Yamagishi, A. Schoonhedyt, R. Persoons, A. and De Schryver, F., 2002 Langmuir-Blodgett Films of a clay meneral and ruthenium(II) complexes with a noncentrosymmetric structure Journal of the American Chemical Society 124 992–997.CrossRefGoogle Scholar
Villemure, G., 1990 Effects of negative charge densities of smectite clays on the adsorption isotherms of racemic and enantiomeric tris(2,2′-bipyridyl)ruthenium(II) chloride Clays and Clay Minerals 38 622–630.CrossRefGoogle Scholar
Yamagishi, A., 1982 Racemic adsorption of tris(1,10-phenanthroline)iron(II) on a colloidally dispersed sodium montmorillonite Journal of Physical Chemistry 86 2474–2479.CrossRefGoogle Scholar
Yamagishi, A., 1985a Chromatographic resolution of enantiomers having aromatic groups by an optically active clay-chelate adduct Journal of the American Chemical Society 107 732–733.CrossRefGoogle Scholar
Yamagishi, A., 1985b Racemic adsorption, anti-racemization and induction of optical activity of metal chelate in the presence of a colloidal clay Inorganic Chemistry 24 1689–1695.CrossRefGoogle Scholar
Yamagishi, A., 1987 Optical resolution and asymmetric syntheses of use of adsorption on clay minerals Review of Coordination Chemistry 16 131–211.CrossRefGoogle Scholar
Yamagishi, A. and Fujita, N., 1984 Racemic adsorption of a bis(chelated)cobalt(III) complex by colloidally dispersed sodium montmorillonite Journal of Colloid and Interface Science 100 136–142.CrossRefGoogle Scholar
Yamagishi, A. and Soma, M., 1981 Optical resolution of metal chelates by use of adsorption on a colloidal clay Journal of the American Chemical Society 103 4640.CrossRefGoogle Scholar
Yamagishi, A. Tanaka, K. and Toyoshima, I., 1982 Auger electron spectroscopic evidence for racemic adsorption of tris(1,10-phenanthroline)iron(II) on sodium montmorillonite Chemical Communications 343–345.CrossRefGoogle Scholar
Yamagishi, A. Taniguchi, M. Imamura, Y. and Sato, H., 1996 Clay column chromatography for optical resolution: selectivities of L-[Ru(phen)3]2+ and L-[Ru(bpy)3]2+ laponite columns towards 1,1′-binaphthol Applied Clay Science 11 1–10.CrossRefGoogle Scholar
Yano, Y. Watanabe, T. Taniguchi, M. and Yamagishi, A., 1992 Electron spin resonance studies on tris(1,10-phenanthroline)copper(II) adsorbed by hectorite and saponite Clay Science 8 381–391.Google Scholar
Yao, Y. Taniguchi, M. Nakata, M. Takahashi, M. and Yamagishi, A., 1998a Nanoscale imaging of molecular adsorption of metal complexes on the surface of a hydrotalcite crystal Langmuir 14 2410–2414.CrossRefGoogle Scholar
Yao, Y. Taniguchi, M. Nakata, M. Takahashi, M. and Yamagishi, A., 1998b Electrochemical scanning tunneling microscopy observation of ordered surface layers on an anionic clay-modified electrode Langmuir 14 2890–2895.CrossRefGoogle Scholar
Yoshida, J. Saruwatari, K. Kameda, J. Sato, H. Yamagishi, A. Sun, L. Corriea, M. and Villemure, G., 2006 Electron transfer through clay monolayer films fabricated by the Langmuir-Blodgett technique Langmuir 22 9591–9597.CrossRefGoogle ScholarPubMed