Abstract
Nanotubes are generally prepared from their constituent elements at high temperatures, and thus it is difficult to control their size, shape and electronic states1,2,3,4,5,6,7,8,9,10. One useful approach for synthesizing well-defined nanostructures involves the use of building blocks such as metal ions and organic molecules11,12,13,14. Here, we show the successful creation of an assembly of infinite square prism-shaped metal–organic nanotubes obtained from the simple polymerization of a square-shaped metal–organic frame. The constituent nanotube has a one-dimensional (1D) channel with a window size of 5.9×5.9 Å2, and can adsorb water (H2O) and alcohol vapours, whereas N2 and CO2 do not adhere. It consists of four 1D covalent chains that constitute a unique electronic structure of ‘charge-density wave (CDW) quartets’ on crystallization. Moreover, exchanging structural components and guest molecules enables us to control its semiconductive bandgap. These findings demonstrate the possibility of bottom-up construction of new porous nanotubes, where their degrees of freedom in both pore space and framework can be used.
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Acknowledgements
Synchrotron XRPD and diffuse X-ray scattering measurements were supported by High Energy Accelerator Research Organization (KEK), Japan (Proposal no. 2008G068). Synchrotron XAFS measurements were supported by Japan Synchrotron Radiation Research Institute (JASRI) (Proposal no. 2010B1975). This work was partly supported by Research Fellowships for Young Scientists (No. 1910614) from the JSPS. H.O. is grateful for support by a Grant-in-Aid for Scientific Research (No. 20110005) by the Ministry of Education, Culture, Sports, Science and Technology of Japan.
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H.K. and K.O. designed and directed this study, and analysed the experimental results. K.O. contributed to all of the experimental work. Y.W. carried out synchrotron diffuse X-ray scattering measurements. J.O. and S.Y. conducted theoretical calculations. H.M. and H.O. contributed to single-crystal reflectance spectroscopy. K.N. and T.U. carried out synchrotron XAFS measurements. K.O., Y.W., J.O., S.Y. and H.K. co-wrote the manuscript. All authors commented on the paper.
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Otsubo, K., Wakabayashi, Y., Ohara, J. et al. Bottom-up realization of a porous metal–organic nanotubular assembly. Nature Mater 10, 291–295 (2011). https://doi.org/10.1038/nmat2963
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DOI: https://doi.org/10.1038/nmat2963