The field of metal-organic framework (MOF) research has been one of the fastest growing new fields of chemistry since its discovery. MOFs combine the predictable and reticular crystal packing of inorganic chemistry with the versatility and tunability of organic chemistry to create materials that allow for structure-property relationships to be studied systematically. Aside from the many promising applications of these materials, one of the more intriguing aspects of MOFs is their ability to incorporate multiple links within the same framework without altering its net. Although this was first demonstrated with Zn-based MOF-5, two main challenges have prevented it from becoming more widely spread among other secondary building units: determining suitable conditions for the thermodynamic crystallization of both links and ensuring the homogeneity of the final multivariate (MTV) MOF. To address this, we have focused on the zirconium-based PEPEP PIZOF (fcu-c) system which has been shown to have a broad range of functionalized linkers that crystallize under the same conditions and synthesized a family of heteroatom-containing links (-F, -I, and -Si), which can be easily probed by SEM-EDX to determine the homogeneity of the MTV MOFs. This work involves a combination of multistep organic synthesis and a solid solution-based, thermodynamically driven crystallization approach to assess the reticular principles of these MTV MOF systems.

Investigating the reticular principles involved in zirconia-based multivariate MOF crystallizations

ACS Spring 2022

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