Vapor-Phase Infiltration inside a Microporous Porphyrinic Metal-Organic Framework for Postsynthesis Modification

Vapor-phase infiltration (VPI), a technique derived from atomic layer deposition (ALD) and based on sequential self-limiting chemistry, is used to modify the stable microporous porphyrin-based metal-organic framework (MOF) MIL-173(Zr). VPI is an appealing approach to modifying MOFs by inserting reactants with atomic precision. The microporous nature and chemical stability of MIL-173 enable postsynthesis modification by VPI without MOF degradation even with extremely reactive precursors such as trimethylaluminum (TMA) and diethylzinc (DEZ). VPI proceeds through the diffusion of gaseous organometallic reactants TMA and DEZ inside the microporous framework, where they react with two kinds of chemical sites offered by the porphyrinic linker (phenolic and pyrrolic functions in the porphyrin core), without altering the crystallinity and permanent porosity of the MOF. ²⁷Al NMR, UV-vis absorption, and IR spectroscopies are used to further characterize the modified material. Physisorption of both precursors is computationally simulated by grand canonical Monte Carlo methods and outlines the preferential adsorption sites. The impact of temperature, number of VPI cycles, and pulse length are investigated and show that aluminum and zinc are introduced in a saturating manner inside the MOF on both available reactive sites. The porosity prerequisite is outlined for VPI, which is proven to be much more effective than classical solution-based methods because it is solventless and fast, prevents workup steps, and allows reactions not possible by the classical solution approach.