Covalent organic frameworks (COFs) formed by connecting multidentate organic building blocks through covalent bonds provide a platform for designing multifunctional porous materials with atomic precision. As they are promising materials for applications in optoelectronics, they would benefit from a maximum degree of long-range order within the framework, which has remained a major challenge. We have developed a synthetic concept to allow consecutive COF sheets to lock in position during crystal growth, and thus minimize the occurrence of stacking faults and dislocations. Hereby, the three-dimensional conformation of propeller-shaped molecular building units was used to generate well-defined periodic docking sites, which guided the attachment of successive building blocks that, in turn, promoted long-range order during COF formation. This approach enables us to achieve a very high crystallinity for a series of COFs that comprise tri- and tetradentate central building blocks. We expect this strategy to be transferable to a broad range of customized COFs.
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We are grateful for funding from the German Science Foundation (Research Cluster Nanosystems Initiative Munich) and the Free State of Bavaria (Research Network SolTech). The research leading to these results received funding from the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013)/ERC Grant Agreement 321339. This research used beamlines 11-BM and 11-ID-B at the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.
The authors declare no competing financial interests.
Supplementary information (PDF 3033 kb)
Crystallographic data obtained by Rietveld refinement for the 4PE-1P COF (CIF 2 kb)
Crystallographic data obtained by Rietveld refinement for the 4PE-2P COF (CIF 2 kb)
Crystallographic data obtained by Rietveld refinement for the 4PE-3P COF (CIF 3 kb)
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Ascherl, L., Sick, T., Margraf, J. et al. Molecular docking sites designed for the generation of highly crystalline covalent organic frameworks. Nature Chem 8, 310–316 (2016). https://doi.org/10.1038/nchem.2444
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