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A nanoporous molecular magnet with reversible solvent-induced mechanical and magnetic properties

Nature Materials volume 2, pages 190–195 (2003)Cite this article

Abstract

Interest in metal–organic open-framework structures has increased enormously in the past few years because of the potential benefits of using crystal engineering techniques to yield nanoporous materials with predictable structures and interesting properties. Here we report a new efficient methodology for the preparation of metal–organic open-framework magnetic structures based on the use of a persistent organic free radical (PTMTC), functionalized with three carboxylic groups. Using this approach, we create an open-framework structure Cu3(PTMTC)2(py)6(CH3CH2OH)2(H2O), which we call MOROF-1, combining very large pores (2.8–3.1 nm) with bulk magnetic ordering. MOROF-1 shows a reversible and highly selective solvent-induced 'shrinking–breathing' process involving large volume changes (25–35%) that strongly influence the magnetic properties of the material. This magnetic sponge-like behaviour could be the first stage of a new route towards magnetic solvent sensors.

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Figure 1: Crystal structure of MOROF-1.
Figure 2: Real images of crystals of MOROF-1 followed with an optical microscope.
Figure 3: Guest exchange studies followed by magnetic and XRPD measurements.
Figure 4: Magnetic properties.

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References

  1. Cheetham, A.K., Férey, G. & Loiseau, T. Open-framework inorganic materials. Angew. Chem. Int. Edn 38, 3269–3292 (1999).

    Article  Google Scholar 

  2. 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 

  3. Zaworotko, M. Nanoporous structures by design. Angew. Chem. Int. Edn 39, 3052–3054 (2000).

    Article  CAS  Google Scholar 

  4. Noro, S.I., Kitagawa, S., Kondo, M. & Seki, K. A new, methane adsorbent, porous coordination polymer [{CuSiF6(4,4'-bipyridine)2}n].Angew. Chem. Int. Edn 12, 2081–2084 (2000).

    Article  Google Scholar 

  5. Xu, X., Nieuwenhuyzen, M. & James, S.L. A nanoporous metal-organic framework based on bulky phosphane ligands. Angew. Chem. Int. Edn 41, 764–767 (2002).

    Article  CAS  Google Scholar 

  6. Bennett, M.V., Beauvais, L.G., Shores, M.P. & Long, J.R. Expanded prussian blue analogues incorporating [Re6Se8(CN)6]3−/4− clusters: adjusting porosity via charge balance. J. Am. Chem. Soc. 123, 8022–8032 (2001).

    Article  CAS  Google Scholar 

  7. Pschirer, N.G., Ciurtin, D.M., Smith, M.D., Bunz, U.H.F. & zur Loye, H.-C. Noninterpenetrating square-grid coordination polymers with dimensions of 25×25Å2 prepared by using N,N'-type ligands: the first chiral square grid coordination polymer. Angew. Chem. Int. Edn 41, 583–586 (2002).

    Article  CAS  Google Scholar 

  8. Chen, B., Eddaoudi, M., Hyde, S.T., O'Keefe, M. & Yaghi, O.M. Interwoven metal-organic framework on a periodic minimal surface with extra-large pores. Science 291, 1021–1023 (2001).

    Article  CAS  Google Scholar 

  9. Barthelet, K., Marrot, J., Riou, D. & Férey, G. A breathing hybrid organic-inorganic solid with very large pores and high magnetic characteristics. Angew. Chem. Int. Edn 41, 281–284 (2002).

    Article  CAS  Google Scholar 

  10. Wynn, C.M., Albrecht, A.S., Landee, C.P., Turnbull, M.M. & Dodrill, B. Resonance in the nonlinear susceptibilities of Co3BTCA2(H2O)4, a molecular-based magnet. J. Solid State Chem. 159, 379–384 (2001).

    Article  CAS  Google Scholar 

  11. Forster, P.M. & Cheetham, A.K. Open-framework nickel succinate, [Ni7(C4H4O4)6(OH)2(H2O)2]·2H2O: a new hybrid material with three dimensional Ni-O-Ni connectivity. Angew. Chem. Int. Edn 41, 457–459 (2002).

    Article  CAS  Google Scholar 

  12. Cotton, F.A., Lin, C. & Murillo, C.A. Supramolecular arrays based on dimetal building units. Acc. Chem. Res. 34, 759–771 (2001).

    Article  CAS  Google Scholar 

  13. Price, D.J., Tripp, S., Powell, A.K. & Wood, P.T. Hydrothermal synthesis, X-ray structure and complex magnetic behaviour of Ba4(C2O4)Cl2[{Fe(C2O4)(OH)}4]. Chem. Eur. J. 7, 200–208 (2001).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  15. Moulton, B., Lu, J., Hajndl, R., Hariharan, S & Zaworotko, M.J. Crystal Engineering of a nanoscale Kagomé lattice. Angew. Chem. Int. Edn 41, 2821–2824 (2002).

    Article  CAS  Google Scholar 

  16. Kim, J. et al. Assembly of metal-organic frameworks from large organic and inorganic secondary building units: new examples and simplifying principles for complex structures. J. Am. Chem. Soc. 123, 8329–8247 (2001).

    Article  Google Scholar 

  17. Eddaoudi, M. et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295, 469–472 (2002).

    Article  CAS  Google Scholar 

  18. Beauvais, L.G. & Long, J.R. Co3[Co(CN)5]2: A microporous magnet with ordering temperature of 38 K. J. Am. Chem. Soc. 124, 12096–12097 (2002).

    Article  CAS  Google Scholar 

  19. Laget, V., Hornick, C., Rabu, P., Drillon, M. & Ziessel, R. Molecular magnets hybrid organic-inorganic layered compounds with very long-range ferromagnetism. Coordin. Chem. Rev. 178, 1533–1553 (1998).

    Article  Google Scholar 

  20. Ballester, M. Inert free radicals: a unique trivalent carbon species. Acc. Chem. Res. 12, 380 (1985).

    Article  Google Scholar 

  21. Pech, R. & Pickardt, J. Catena-triaqua-μ-[1,3,5-benzenetricarboxylato(2-)]-copper(II). Acta Cryst. C 44, 992–994 (1988).

    Article  Google Scholar 

  22. Abourahma, H., Moulton, B., Kravtsov, V. & Zaworotko, M.J. Supramolecular isomerism in coordination compounds: nanoscale molecular hexagons and chains. J. Am. Chem. Soc. 124, 9990–9991 (2002).

    Article  CAS  Google Scholar 

  23. Min, K.S. & Suh, M.P. Self-assembly and selective guest binding of three-dimensional open-framework solids form a macrocyclic complex as a trifunctional metal building block. Chem. Eur. J. 7, 303–313 (2001).

    Article  CAS  Google Scholar 

  24. Lu, J.Y. & Babb, A.M. An extremely stable open-framework metal-organic polymer with expandable structure and selective adsorption capability. Chem. Commun. 1340–1341 (2002).

  25. Kitagawa, S. et al. Novel flexible frameworks of porous (II) coordination polymers that show selective guest adsorption based on the switching of hydrogen-bond pairs of amide groups. Chem. Eur. J. 8, 3587–3600 (2002).

    Google Scholar 

  26. Biradha, K. & Fujita, M. A springlike 3D-coordination network that shrinks or swells in a crystal-to-crystal manner upon guest removal or re-adsorption. Angew. Chem. Int. Edn 41, 3392–3395 (2002).

    Article  CAS  Google Scholar 

  27. 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)3·6H2O (BDC=1,4-benzene dicarboxylate). J. Am. Chem. Soc. 120, 2186–2187 (1998).

    Article  CAS  Google Scholar 

  28. Maspoch, D., Ruiz-Molina, D., Wurst, K., Rovira, C. & Veciana, J. A very bulky carboxylic perchlorotriphenylmethyl radical as a novel ligand for transition metal complexes. A new spin frustrated metal system. Chem. Commun. 2958–2959 (2002).

  29. Larionova, J., Mombelli, B., Sanchiz, J. & Kahn, O. Magnetic properties of the two-dimensional bimetallic compounds (NBu4)[MIIRuIII(ox)3] (NBu4=Tetra-n-butylammonium; M=Mn, Fe, Cu; ox=oxalate). Inorg. Chem. 37, 679–684 (1998).

    Article  CAS  Google Scholar 

  30. Kahn, O. in Molecular Magnetism (ed. Kahn, O.) 251–332 (VCH, New York, 1993).

    Google Scholar 

  31. Caneschi, A., Gatteschi, D., Lalioti, N., Sangregorio, C. & Sessoli, R. Supramolecular interactions and magnetism of metal-radical chains. J. Chem. Soc. Dalton Trans. 2000, 3907–3912 (2000).

    Article  Google Scholar 

  32. Ivamura, H. & Inoue, K. in Magnetism: Molecules to Materials Vol. III (eds Miller, J.S. & Drillon, M.) 61–108 (Wiley-VCH, Weinheim, 2001).

    Book  Google Scholar 

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Acknowledgements

This work was supported by the Programa Nacional de Materiales of the Dirección General de Investigación (Spain), under project MAGMOL. D.M. is grateful to the Generalitat de Catalunya for a predoctoral grant. We thank P. Gerbier of the Université Montpellier for TG-MS experiments and X. Alcobé of the Universitat de Barcelona for X-ray powder diffraction measurements.

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Authors and Affiliations

  1. Institut de Ciència de Materials de Barcelona (CSIC), Campus Universitari de Bellaterra, Cerdanyola, 08193, Spain

    Daniel Maspoch, Daniel Ruiz-Molina, Concepció Rovira & Jaume Veciana

  2. Institut für Allgemeine, Anorganische und Theoretische Chemie, Universität Innsbruck, Innrain 52a, Innsbruck, A-6020, Austria

    Klaus Wurst

  3. Facultad de Física, Universitat de Barcelona, Diagonal 647, Barcelona, 08028, Spain

    Neus Domingo & Javier Tejada

  4. CNR-Istituto per lo Studio dei Materiali Nanostrutturati (CNR), Via P. Gobetti 101, Bologna, I-40129, Italy

    Massimilliano Cavallini & Fabio Biscarini

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  1. Daniel Maspoch
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Correspondence to Jaume Veciana.

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Supplementary information

Figure 1S Magnetization value as a function of the applied field at a temperature of 2.5 K for MOROF-1

Figure 2S Reversible magnetic behavior of the amorphous and evacuated phase in contact with ethanol liquid, plot of magnetization value as a function of the applied field at a temperature of 2.5 K (PDF 891 kb)

Figure 3S Plots of χ'MT (top) and χ"MT (bottom) as a function of the temperature for MOROF-1 at the indicated frequencies

Figure 4S χT value as a function of the temperature for MOROF-1

Figure 5S (Left) χT value as a function of the temperature for complex Cu(PTMMC)2(H2O)3.

Figure 6S  Powder X-ray diffractogram of MOROF-1 (red) and MOOF-1 (black).

Structure The crystal structure of MOROF-1.

Movie 1 This video shows the "shrinking-breathing" process. (AVI 745 kb)

Movie 2 This video shows the shrinking process of one crystal followed with polarized light. (AVI 2002 kb)

Movie 3 This video shows the breathing process of one crystal followed with polarized light. (GIF 2403 kb)

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Maspoch, D., Ruiz-Molina, D., Wurst, K. et al. A nanoporous molecular magnet with reversible solvent-induced mechanical and magnetic properties. Nature Mater 2, 190–195 (2003). https://doi.org/10.1038/nmat834

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