Abstract
Many molecular cages selectively bind guests in solution, but in the solid state close packing often prevents guest entry, which renders the cages inactive. We envisioned that coordination networks constructed from well-known molecular cages could transfer the richness of solution-state host–guest chemistry into the solid state. We report a crystalline coordination network generated from an infinite array of octahedral M6L4 cage subunits (M = metal, L = ligand). This coordination network is a ‘crystalline molecular sponge’ engineered on the molecular level and retains similar guest recognition properties to those found in solution. The network crystallinity is robust and thus X-ray diffraction analysis can be used to unambiguously observe single-crystal to single-crystal guest inclusion. The void spaces define alternating M12L8 and M12L24 cuboctahedral molecular cages and these large cages absorb up to 35 weight per cent of C60 or C70 by simply soaking the crystals in a toluene solution of the fullerene. When the crystals are immersed in fullerene mixtures, C70 is preferentially absorbed.
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References
Yaghi, O. M. et al. Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003).
Kitagawa, S., Kitaura, R. & Noro, S. Functional porous coordination polymers. Angew. Chem. Int. Ed. 43, 2334–2375 (2004).
Lehn, J.-M. Supramolecular Chemistry (VCH, 1995).
Li, Q. et al. Docking in metal–organic frameworks. Science 325, 855–859 (2009).
Hof, F., Craig, S. L., Nuckolls, C. & Rebek, J. Jr Molecular encapsulation. Angew. Chem. Int. Ed. 41, 1488–1508 (2002).
Caulder, D. L. & Raymond, K. N. Supermolecules by design. Acc. Chem. Res. 32, 975–982 (1999).
Yoshizawa, M., Klosterman, J. K. & Fujita, M. Functional molecular flasks: new properties and reactions within discrete, self-assembled hosts. Angew. Chem. Int. Ed. 48, 3418–3438 (2009).
Fujita, M. et al. Self-assembly of ten molecules into nanometre-sized organic host frameworks. Nature 378, 469–471 (1995).
Wang, X.-S., Ma, S., Sun, D., Parkin, S & Zhou, H.-C. A mesoporous metal–organic framework with permanent porosity. J. Am. Chem. Soc. 128, 16474–16475 (2006).
Abrahams, B. F., Batten, S. R., Hamit, H., Hoskins, B. F. & Robson, R. A cubic (3,4)-connected net with large cavities in solvated [Cu3(tpt)4](ClO4)3 (tpt=2,4,6-tri(4-pyridyl)-1,3,5-triazine). Angew. Chem. Int. Ed. 35, 1690–1692 (1996).
Ohmori, O., Kawano, M. & Fujita, M. Crystal-to-crystal guest exchange of large organic molecules within a 3D coordination network. J. Am. Chem. Soc. 126, 16292–16293 (2004).
Kawano, M. & Fujita, M. Direct observation of crystalline-state guest exchange in coordination networks. Coord. Chem. Rev. 251, 2592–2605 (2007).
Sato, S. et al. Fluorous nanodroplets structurally confined in an organopalladium sphere. Science 313, 1273–1276 (2006).
Chae, H. K. et al. A route to high surface area, porosity and inclusion of large molecules in crystals. Nature 427, 523–527 (2004).
Krätschmer, W., Lamb, L. D., Fostiropoulos, K. & Huffman, D. R. Solid C60: a new form of carbon. Nature 347, 354–358 (1990).
Kikuchi, K. et al. NMR characterization of isomers of C78, C82 and C84 fullerenes Nature 357, 142–145 (1992).
Diener, M. D. & Alford, J. M. Isolation and properties of small-bandgap fullerenes. Nature 393, 668–671 (1998).
Huerta, E. et al. Selective binding and easy separation of C70 by nanoscale self-assembled capsules. Angew. Chem. Int. Ed. 46, 202–205 (2007).
Shoji, Y., Tashiro, K. & Aida, T. Selective extraction of higher fullerenes using cyclic dimers of zinc porphyrins. J. Am. Chem. Soc. 126, 6570–6571 (2004).
Vandersluis, P. & Spek, A. L. Bypass: an effective method for the refinement of crystal structures containing disordered solvent regions. Acta Crystallogr. A 46, 194–201 (1990).
Acknowledgements
This research was supported in part by KAKENHI, Japan Society for the Promotion of Science.
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Y.I. and M.F. designed the project, analysed the results and co-wrote the manuscript. T.A. carried out the experimental work.
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Crystallographic data for 1 (CIF 14 kb)
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Crystallographic data for 1⊃(TTF)n (CIF 23 kb)
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Crystallographic data for 1⊃(Ph2NH)n (CIF 50 kb)
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Crystallographic data for 2⊃(TTF)4 (CIF 29 kb)
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Inokuma, Y., Arai, T. & Fujita, M. Networked molecular cages as crystalline sponges for fullerenes and other guests. Nature Chem 2, 780–783 (2010). https://doi.org/10.1038/nchem.742
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DOI: https://doi.org/10.1038/nchem.742
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