307514-65-4Relevant academic research and scientific papers
Non-Interpenetrated Single-Crystal Covalent Organic Frameworks
Han, Jing,Liang, Lin,Luo, Yi,Ma, Tianqiong,Ni, Jianwei,Niu, Jing,Qiu, Yi,Sun, Junliang,Wang, Wei,Wang, Wei David,Wang, Zhi-Peng,Yin, Guan-Lin,Yu, Wei,Zhang, Lei
, p. 17991 - 17995 (2020)
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 2H NMR investigation has determined that the rotation of benzene rings in TPE, being the freest among the reported cases, is as fast as 1.0×104 Hz at 203 K to 1.5×107 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.
Phenyl ring dynamics in a tetraphenylethylene-bridged metal-organic framework: Implications for the mechanism of aggregation-induced emission
Shustova, Natalia B.,Ong, Ta-Chung,Cozzolino, Anthony F.,Michaelis, Vladimir K.,Griffin, Robert G.,Dinca, Mircea
, p. 15061 - 15070,10 (2020/08/24)
Molecules that exhibit emission in the solid state, especially those known as aggregation-induced emission (AIE) chromophores, have found applications in areas as varied as light-emitting diodes and biological sensors. Despite numerous studies, the mechanism of fluorescence quenching in AIE chromophores is still not completely understood. To this end, much interest has focused on understanding the low-frequency vibrational dynamics of prototypical systems, such as tetraphenylethylene (TPE), in the hope that such studies would provide more general principles toward the design of new sensors and electronic materials. We hereby show that a perdeuterated TPE-based metal-organic framework (MOF) serves as an excellent platform for studying the low-energy vibrational modes of AIE-type chromophores. In particular, we use solid-state 2H and 13C NMR experiments to investigate the phenyl ring dynamics of TPE cores that are coordinatively trapped inside a MOF and find a phenyl ring flipping energy barrier of 43(6) kJ/mol. DFT calculations are then used to deconvolute the electronic and steric contributions to this flipping barrier. Finally, we couple the NMR and DFT studies with variable-temperature X-ray diffraction experiments to propose that both the ethylenic C' - 'C bond twist and the torsion of the phenyl rings are important for quenching emission in TPE, but that the former may gate the latter. To conclude, we use these findings to propose a set of design criteria for the development of tunable turn-on porous sensors constructed from AIE-type molecules, particularly as applied to the design of new multifunctional MOFs.
