Water-soluble arylphosphines (Ar3P) and arylarsines (Ar3As) are ubiquitous in biphasic organometallic catalysis. They are also ideal precursors for the construction of hybrid organic-inorganic porous polymer materials. The resulting periodic, crystalline materials can be chemically modified in the solid-state, in a variety of ways, to decorate the pores with chemical moieties that induce unique guest selectivity behavior, small molecule sensing and catalysis. By using pillaring techniques during synthesis, we can prepare cavities inside MOFs that are decorated with multiple P: sites arranged in trans- or cis-orientations, to generate coordiantion pockets that mimic ligands used in organometallic catalysis. Yet, the structural rigidity imposed by the MOF also restricts movement of the P: sites, thus potentially allowing for the preparation of coordination complexes in which the metal-ligand bond distaces are non-equilibrium (i.e., comressively or extensively strained). In turn, results in catalytic activity that is different than what is observed in solution for the classical, molecular species.

Phosphine, arsine and related metal-organic frameworks: Unique catalyst support materials

256th National Meeting (2018)

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