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Constructing monocrystalline covalent organic networks by polymerization
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Constructing monocrystalline covalent organic networks by polymerization
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Journal Article
Constructing monocrystalline covalent organic networks by polymerization
2013
Overview
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.
Modular construction using connectable molecular subunits is a powerful strategy for making new carbon-based materials. So far, large crystals have been produced only from subunits linked by weak interactions. Covalently bonded analogues have now been prepared by reversible self-addition polymerization of suitable monomers and structurally characterized by single-crystal X-ray diffraction.
