Incorporation of guest molecules that are larger than the aperture size of zeolitic imidazolate metal organic frameworks (e.g. ZIF-8) is made possible by taking advantage of ligand substitution reactions that lead to linker exchange in ZIF-8.   Incubating rhodamine-G6 dye with commercially prepared ZIF-8 under conditions where linker exchange occurs leads to incorporation of the dye in the metal organic framework despite the fact that its diameter (~11 �) is significantly larger than the aperture size of ZIF-8 (3.4 �).  Through mechanistic studies, it was shown that incorporation of the large guest molecules is possible due to a dissociative ligand substitution mechanism.  Such a mechanism leads to an intermediate that is significantly more �open� than the apertures in isolated ZIF-8.  The generality of this route for guest incorporation will be discussed along with potential applications in catalysis and imaging.

Large guest incorporation in ZIF-8 metal organic framework facilitated by dissociative ligand substitution reactions

248th National Meeting (2014)

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