Molecular Encapsulation beyond the Aperture Size Limit through Dissociative Linker Exchange in Metal鈥揙rganic Framework Crystals
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- 作者：Joseph V. Morabito ; Lien-Yang Chou ; Zhehui Li ; Cesar M. Manna ; Christopher A. Petroff ; Rutvin J. Kyada ; Joseph M. Palomba ; Jeffery A. Byers ; Chia-Kuang Tsung
- 刊名：Journal of the American Chemical Society
- 出版年：2014
- 出版时间：September 10, 2014
- 年：2014
- 卷：136
- 期：36
- 页码：12540-12543
- 全文大小：291K
- ISSN：1520-5126
文摘
Under linker exchange conditions, large guests with molecular diameters 3鈥? times the framework aperture size have been encapsulated into preformed nanocrystals of the metal鈥搊rganic framework ZIF-8. Guest encapsulation is facilitated by the formation of short-lived 鈥渙pen鈥?states of the pores upon linker dissociation. Kinetic studies suggested that linker exchange reactions in ZIF-8 proceed via a competition between dissociative and associative exchange mechanisms, and guest encapsulation was enhanced under conditions where the dissociative pathway predominates.