Numerous strategies for the synthesis of multicomponent metal-organic framework (MOF) pores have been reported, but these strategies lack the coupled structural versatility and molecular precision required to generate well-defined reactive sites. Here, I will describe a highly generalizable strategy for templating pairwise sites within MOF pores. Using a thermolabile tertiary ester crosslinker, we have templated carboxylic acid pairs within the mesoporous, terphenyl expanded analogue of Mg-MOF-74. Spectroscopic, diffraction, and adsorption data confirm the incorporation and subsequent removal of the crosslinker occurs without disrupting the framework, while computational studies confirm that short alkyl chain lengths restrict the acid pairs to a single conformation within the pores, thus generating site-isolated pairs at low crosslinker concentration. Our templating strategy is readily extended to functional groups beyond carboxylic acid pairs. We have also developed a tertiary carbamate crosslinker for templating pairwise amine sites. Postsynthetic functionalization of the amines and subsequent metalation allows us to access site isolated transition metal pairs. Progress towards templated acid-base will also be described.

Precise templating of multicomponent metal-organic framework pores

ACS Spring 2022

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