Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

A homochiral metal–organic porous material for enantioselective separation and catalysis

Nature volume 404, pages 982–986 (2000)Cite this article

Abstract

Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics1,2,3, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced14,15, and investigations into the range of accessible pore functionalities have been initiated7,11,12,16,17,18,19,20,21,22,23. For example, catalytically active organic zeolite analogues are known13,22,23, as are chiral metal–organic open-framework materials. However, the latter are only available as racemic mixtures24,25, or lack the degree of framework stability or void space that is required for practical applications26,27. Here we report the synthesis of a homochiral metal–organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal–organic clusters as secondary building blocks14, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1
Figure 2: Structure of the trinuclear secondary building unit.
Figure 3: The hexagonal framework with large pores that is formed with the trinuclear secondary building units.
Figure 4: View down the c axis showing large chiral channels of POST-1.
Figure 5: Catalytic activity of POST-1 in transesterification reactions.

Similar content being viewed by others

References

  1. Yaghi,O. M., Li,H., Davis,C, Richardson,D. & Groy, T. L. Synthetic strategies, structure patterns, and emerging properties in the chemistry of modular porous solids. Acc. Chem. Res. 31, 474–484 ( 1998).

    Article  CAS  Google Scholar 

  2. Aoyama,Y. Functional organic zeolite analogues. Top. Curr. Chem. 198, 131–161 (1998).

    Article  CAS  Google Scholar 

  3. Kitagawa,S. & Kondo,M. Functional micropore chemistry of crystalline metal complex-assembled compounds. Bull. Chem. Soc. Jpn 71, 1739–1753 (1998).

    Article  CAS  Google Scholar 

  4. Janiak,C. Functional organic analogues of zeolites based on metal-organic coordination frameworks. Angew. Chem. Int. Edn Engl. 36, 1431–1434 (1997).

    Article  CAS  Google Scholar 

  5. Abrahams,B. F., Hoskins,B. F., Michail,D. M. & Robson,R. Assembly of porphyrin building blocks into network structures with large channels. Nature 369, 727–729 (1994).

    Article  ADS  CAS  Google Scholar 

  6. Yaghi,O. M., Li,G. & Li,H. Selective binding and removal of guests in a microporous metal-organic framework. Nature 378, 703–706 (1995).

    Article  ADS  CAS  Google Scholar 

  7. Aoyama,Y. et al. Crystal engineering of stacked aromatic columns. Three-dimensional control of the alignment of orthogonal aromatic triads and guest quinones via self-assembly of hydrogen-bonded networks. J. Am. Chem. Soc. 118, 5562–5571 ( 1996).

    Article  CAS  Google Scholar 

  8. Gardner,G. B., Venkataraman,D., Moore,J. S. & Lee,S. Spontaneous assembly of a hinged coordination network. Nature 374 , 792–795 (1995).

    Article  ADS  CAS  Google Scholar 

  9. Subramanian,S. & Zaworotko,M. J. Porous solids by design: [Zn(4,4′-bipy) 2(SiF6)]n·xDMF, a single framework octahedral coordination polymer with large square channels. Angew. Chem. Int. Edn Engl. 34, 2127–2129 (1995).

    Article  CAS  Google Scholar 

  10. Russell,V. A., Evans,C. C., Li,W. & Ward,M. D. Nanoporous molecular sandwiches: pillared two-dimensional hydrogen-bonded networks with adjustable porosity. Science 276, 575– 579 (1997).

    Article  CAS  Google Scholar 

  11. Brunet,P., Simart,M. & Wuest,J. D. Molecular tectonics. Porous hydrogen-bonded networks with unprecedented structural integrity. J. Am. Chem. Soc. 119, 2737–2738 (1997).

    Article  CAS  Google Scholar 

  12. Fujita,M., Kwon,Y. J., Washizu,S. & Ogura,K. Preparation, clathration ability, and catalysis of a two-dimensional square network material composed of cadmium(II) and 4,4′-bipyridine. J. Am. Chem. Soc. 116, 1151–1152 (1994).

    Article  CAS  Google Scholar 

  13. Heo,J., Kim,S. Y., Whang,D. & Kim,K. Shape-induced, hexagonal, open frameworks: rubidium ion complexed cucurbituril. Angew. Chem. Int. Edn 38, 641–643 ( 1999).

    Article  CAS  Google Scholar 

  14. Li,H., Eddaoudi,M., O'Keeffe,M. & Yaghi,O. M. Design and synthesis of an exceptionally stable and highly porous metal-organic framework. Nature 402, 276–279 ( 1999).

    Article  ADS  CAS  Google Scholar 

  15. Chui,S. S.-Y., Lo,S. M.-F., Charmant,J. P. H., Orpen,A. G. & Williams,I. D. A chemically functionallizable nanoporous material [Cu3(TMA)2(H2O) 3]n. Science 283, 1148–1150 (1999).

    Article  ADS  CAS  Google Scholar 

  16. Kiang,Y.-H., Gardner,G. B., Lee,S., Xu,Z. & Lobkovsky,E. B. Variable pore size, variable chemical functionality, and an example of reactivity within porous phenylacetylene silver salts. J. Am. Chem. Soc. 121, 8204–8215 (1999).

    Article  CAS  Google Scholar 

  17. Gardner,G. B., Kiang,Y.-H., Lee,S., Asgaonkar,A. & Venkataraman, D. Exchange properties of the three-dimensional coordination compound 1,3,5-Tris(4-ethynylbenzonitrile)benzene·AgO3SCF 3. J. Am. Chem. Soc. 118, 6946– 6953 (1996).

    Article  CAS  Google Scholar 

  18. Lin,K.-J. SMTP-1: the first functionalized metalloporphyrin molecular sieves with large channels. Angew. Chem. Int. Edn 38, 2730 –2732 (1999).

    Article  CAS  Google Scholar 

  19. Li,H., Davis,C. E., Groy,T. L., Kelley,D. G. & Yaghi, O. M. Coordinatively unsaturated metal centers in the extended porous framework of Zn3(BDC)3·6CH3OH (BDC = 1,4-Benzenedicarboxylate). J. Am. Chem. Soc. 120, 2186–2187 (1998).

    Article  CAS  Google Scholar 

  20. Reineke,T. M., Eddaoudi,M., Fehr,M., Kelley,D. & Yaghi,O. M. From condensed lanthanide coordination solids to microporous frameworks having accessible metal sites. J. Am. Chem. Soc. 121, 1651–1657 (1999).

    Article  CAS  Google Scholar 

  21. Kondo,K., Yoshitomi,T., Seki,K., Matsuzaka,H. & Kitagawa, S. Three-dimensional framework with channeling cavities for small molecules: {[M2(4,4′-bpy)3(NO3 )4]·xH2O}n (M = Co, Ni, Zn). Angew. Chem. Int. Edn Engl. 36, 1725– 1727 (1997).

    Article  CAS  Google Scholar 

  22. Endo,K. et al. Catalysis by organic solids. Stereoselective Diels–Alder reactions promoted by microporous molecular crystals having an extensive hydrogen-bonded network. J. Am. Chem. Soc. 119, 4117– 4122 (1997).

    Article  CAS  Google Scholar 

  23. Sawaki,T. & Aoyama,Y. Immobilization of a soluble metal complex in an organic network. Remarkable catalytic performance of a porous dialkoxyzirconium polyphenoxide as a functional organic zeolite analogue. J. Am. Chem. Soc. 121, 4793– 4798 (1999).

    Article  CAS  Google Scholar 

  24. Biradha,K., Seward,C. & Zaworotko, M. J. Helical coordination polymers with large chiral cavities. Angew. Chem. Int. Edn Engl. 38, 492– 495 (1999).

    Article  CAS  Google Scholar 

  25. Decurtins,S., Schmalle,H. W., Schneuwly, P., Ensling,J. & Gütlich,P. A concept for the synthesis of 3-dimensional homo- and bimetallic oxalate-bridged networks [M2(ox) 3]n. Structural, Mössbauer, and magnetic studies in the field of molecular-based magnets. J. Am. Chem. Soc. 116, 9521–9528 (1994).

    Article  CAS  Google Scholar 

  26. Normar,R. E., Rose,N. J. & Stenkamp, R. E. Crystal structure of a copper complex of 2-carboxypentonic acid; a decomposition product of dehydroascorbic acid. J. Chem. Soc. Dalton Trans. 2905–2910 ( 1987).

  27. Ranford,J. D., Vittal,J. J. & Wu,D. Topochemical conversion of a hydrogen-bonded three-dimensional network into a covalently bonded framework. Angew. Chem. Int. Edn Engl. 37, 1114–1116 (1998).

    Article  CAS  Google Scholar 

  28. Hathaway,B. J. in Comprehensive Coordination Chemistry Vol. 2 (ed. Wilkinson, G.) 439–441 (Pergamon, Oxford, 1987).

    Google Scholar 

Download references

Acknowledgements

We thank the Korean Ministry of Science and Technology (Creative Research Initiatives Program) for supporting this work and the Korean Ministry of Education (Brain Korea 21 program) for graduate student fellowships (J.O. and Y.J.J.). We also thank M. G. Finn and L. K. Woo for critical reading of the manuscript.

Author information

Authors and Affiliations

  1. National Creative Research Initiative Center for Smart Supramolecules and Department of Chemistry, Division of Molecular and Life Sciences, Pohang University of Science and Technology, San 31 Hyojadong, Pohang, 790-784, Republic of Korea

    Jung Soo Seo, Dongmok Whang, Hyoyoung Lee, Sung Im Jun, Jinho Oh, Young Jin Jeon & Kimoon Kim

Authors
  1. Jung Soo Seo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dongmok Whang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hyoyoung Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Sung Im Jun
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jinho Oh
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Young Jin Jeon
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Kimoon Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kimoon Kim.

Supplementary information

Rights and permissions

Reprints and permissions

About this article

Cite this article

Seo, J., Whang, D., Lee, H. et al. A homochiral metal–organic porous material for enantioselective separation and catalysis. Nature 404, 982–986 (2000). https://doi.org/10.1038/35010088

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/35010088

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing