Porous coordination polymers (PCPs) that employ phosphine-based linkers have shown promising results in applications such as gas storage, separations, and molecular sensing materials. The incorporation of R3P: sites into a PCP allows access to a wide range of P(III)‒P(V) chemistry for increased versatility and tunability of the framework structures. These sites can be exploited in a range of unusual organic and inorganic modifications both pre- and post-synthetically. In the new work presented, tetrahedral organophosphonium ligands have been reacted with a variety of alkali earth metals, early transition metals, and lanthanides to produce a new family of Phosphine Coordination Materials (PCMs). A series of five PCMs were synthesized using the linker ([H3C)P(C6H4-p-CO2H)3]Cl) [mptbcH3]Cl with Zn(OAc)2∙2H2O in a 4:1:1 (DMF:EtOH:H2O) solution, along with the variation of alkali hydroxide (Li, Na, K, Rb, or Cs). The tetrahedral phosphonium linker employed acts as a trigonal connector in the resulting materials, and was effective in the formation of arrays of fused M2L2 molecular squares. Each of the frameworks were characterized via single crystal x-ray diffraction, powder x-ray diffraction, thermogravometric analysis, elemental analysis, and BET analysis. All five frameworks have relatively high internal surface areas within the field of PCMs ranging between 800-1150 m2/g. A new series of bis(phosphine) linkers are also being developed to allow for a larger range of possible post-synthetic modifications. An example of PCMs based on these tailored systems include PCM-18, which uses a benzene backbone linker with Zinc nodes. These frameworks occur in a wide assortment of topologies and pore functionalities, with unusual solid-state properties.

Novel phosphine coordination materials based on bis(phosphine) and methyl triarylphosphonium groups for applications in gas storage, separations, and sensing

249th National Meeting (2015)

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