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(一)nature
(二)nature chemistry
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Networked molecular cages as crystalline sponges for fullerenes and other guests
●Yasuhide Inokuma1,
●Tatsuhiko Arai1 &
●Makoto Fujita1,2
Nature Chemistry
volume 2, pages 780–783 (2010)Cite this article
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310 Citations
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Subjects
●Carbon nanotubes and fullerenes
●Coordination chemistry
●Inorganic chemistry
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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Figure 1: Octahedral cages as infinite networks and discrete molecular hosts.
Figure 2: Crystal structures of TTF encapsulated by infinite and discrete M6L4 cages.
Figure 3: Three distinct polyhedral molecular cages in the infinite crystalline network 1.
Figure 4: The inclusion of C60 into the crystalline network 1.
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Acknowledgements
This research was supported in part by KAKENHI, Japan Society for the Promotion of Science.
Author information
Authors and Affiliations
Department of Applied Chemistry, School of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan
Yasuhide Inokuma, Tatsuhiko Arai & Makoto Fujita
Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan
Makoto Fujita
Authors
(一)Yasuhide Inokuma
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(二)Tatsuhiko Arai
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(三)Makoto Fujita
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Contributions
Y.I. and M.F. designed the project, analysed the results and co-wrote the manuscript. T.A. carried out the experimental work.
Corresponding author
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Makoto Fujita.
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The authors declare no competing financial interests.
Supplementary information
Supplementary information (PDF 1183 kb)
Crystallographic data for 1(CIF 14 kb)
Crystallographic data for 1⊃(TTF)n (CIF 23 kb)
Crystallographic data for 1⊃(Ph2NH)n (CIF 50 kb)
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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