The development of porous coordination polymers that incorporate uncommon organic moieties has received recent attention as a means to functionalise internal pore surfaces for specific applications in selective sorption of small molecules. Coordination materials that contain available Lewis base sites are of particular interest because they are convenient for direct post-synthetic modification. For instance, via post-synthetic attachment of catalytic metal species. The use of triarylphosphines as Lewis base ligands is well known in coordination chemistry. However, there are just few examples or their application in the design and synthesis of functional coordination polymers. Phosphine ligands are ideal candidates for the constructions of new functional coordination polymers for several additional reasons that include the broad range of P(III) to P(V) chemistry which provides access to polar (e.g. R3PE (E = O, S, NR, BX3, etc.) or ionic substituents (e.g. [R3PR]+). Phosphine Coordination Materials (PCMs) are porous coordination polymers based on organophosphine ligands which have been studied previously within our group and recently have afforded very interesting gas adsorption results and catalytic activity. PCM-10 is a porous phosphine coordination material based on Ca(II) and tris(p-carboxylated) triphenylphosphine that shows the unusual ability to selectively adsorb 1-hexene over n-hexane at room temperature and more interestingly, this material shows catalitic activity on the addition of phenols and carboxylic acids accross a double bound. PCM-11 is a three dimensional framework structure constructed by the reaction of Mg(II) with tris(para-carboxylato)triphenylphosphine oxide. PCM-11 is easily activated for small molecule sorption at low temperature without the requirement for solvent pre-exchange.  It adsorbs 47.5 wt% CO2 at 11.6 bar and 30 �C. PCM-14, a Ca(II)-based material, presents an unusual crystal structure and after an appropriate sample activation, it shows significant CO2 selectivity over other gases like N2 and O2.

Phosphine coordination materials for versatile solid-state applications

244th National Meeting (2012)

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