Abstract
An emerging strategy for making ordered materials is modular construction, which connects preformed molecular subunits to neighbours through interactions of properly selected reactive sites. This strategy has yielded remarkable materials, including metal–organic frameworks joined by coordinative bonds, supramolecular networks linked by strong non-covalent interactions, and covalent organic frameworks in which atoms of carbon and other light elements are bonded covalently. However, the strategy has not yet produced covalently bonded organic materials in the form of large single crystals. Here we show that such materials can result from reversible self-addition polymerizations of suitably designed monomers. In particular, monomers with four tetrahedrally oriented nitroso groups polymerize to form diamondoid azodioxy networks that can be fully characterized by single-crystal X-ray diffraction. This work forges a strong new link between polymer science and supramolecular chemistry by showing how predictably ordered covalent or non-covalent structures can both be built using a single modular strategy.
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Acknowledgements
The authors acknowledge the Natural Sciences and Engineering Research Council of Canada, the Ministère de l’Éducation du Québec, the Canada Foundation for Innovation, the Canada Research Chairs Program and Université de Montréal for financial support.
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D.B. synthesized and crystallized all new compounds, and he also carried out all analyses except for the crystallographic studies. T.M. collected, processed and refined all crystallographic data. All authors discussed the results and contributed to the preparation of the manuscript.
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Supplementary information (PDF 1780 kb)
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Crystallographic data for compound 1. (CIF 14 kb)
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Crystallographic data for compound NPN1. (CIF 13 kb)
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Crystallographic data for compound NPN2. (CIF 13 kb)
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Crystallographic data for compound NPN3. (CIF 15 kb)
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Beaudoin, D., Maris, T. & Wuest, J. Constructing monocrystalline covalent organic networks by polymerization. Nature Chem 5, 830–834 (2013). https://doi.org/10.1038/nchem.1730
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DOI: https://doi.org/10.1038/nchem.1730
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