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- Liang, Lin, et al.
(författare)
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Non-Interpenetrated Single-Crystal Covalent Organic Frameworks
- 2020
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 59:41, s. 17991-17995
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Tidskriftsartikel (refereegranskat)abstract
- Growth of covalent organic frameworks (COFs) as single crystals is extremely challenging. Inaccessibility of open-structured single-crystal COFs prevents the exploration of structure-oriented applications. Herein we report for the first time a non-interpenetrated single-crystal COF, LZU-306, which possesses the open structure constructed exclusively via covalent assembly. With a high void volume of 80 %, LZU-306 was applied to investigate the intrinsic dynamics of reticulated tetraphenylethylene (TPE) as the individual aggregation-induced-emission moiety. Solid-state(2)H NMR investigation has determined that the rotation of benzene rings in TPE, being the freest among the reported cases, is as fast as 1.0x10(4) Hz at 203 K to 1.5x10(7) Hz at 293 K. This research not only explores a new paradigm for single-crystal growth of open frameworks, but also provides a unique matrix-isolation platform to reticulate functional moieties into a well-defined and isolated state.
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| 2. |
- Xu, Hai-Sen, et al.
(författare)
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Single crystal of a one-dimensional metallo-covalent organic framework
- 2020
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 11:1
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Tidskriftsartikel (refereegranskat)abstract
- Although polymers have been studied for well over a century, there are few examples of covalently linked polymer crystals synthesised directly from solution. One-dimensional (1D) covalent polymers that are packed into a framework structure can be viewed as a 1D covalent organic framework (COF), but making a single crystal of this has been elusive. Herein, by combining labile metal coordination and dynamic covalent chemistry, we discover a strategy to synthesise single-crystal metallo-COFs under solvothermal conditions. The single-crystal structure is rigorously solved using single-crystal electron diffraction technique. The non-centrosymmetric metallo-COF allows second harmonic generation. Due to the presence of syntactic pendant amine groups along the polymer chains, the metallopolymer crystal can be further cross-linked into a crystalline woven network. Although polymers have been studied for well over a century, there are few examples of covalently linked polymer crystals synthesized directly from solution. Here, the authors demonstrate a strategy to synthesize single crystalline 1D metallo-covalent organic frameworks by combining dynamic covalent chemistry and metal-ligand coordination.
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