A new Mg(II) -based version of the porous coordination polymer CUK-1 with one-dimensional pore structure was prepared by microwave synthesis in water. Mg-CUK-1 is moisture-stable, thermally stable up to 500 °C, and shows unusual reversible soft-crystal behavior: dehydrated single crystals of the material selectively adsorb a range of organic molecules at ambient temperature and pressure. Both polar and apolar aromatic compounds, including pyridine, benzene, p-xylene, and p-divinylbenzene (p-DVB), are all readily adsorbed, while other isomers from complex mixtures of xylenes or DVBs are selectively excluded. The solvent-loaded structures have been studied by single-crystal X-ray diffraction. Time-dependent liquid sorption experiments using commercially available DVB demonstrate a high and rapid selective adsorption of p-DVB and exclusion of m-DVB and ethylvinylbenzene isomers.
MCl2 complexes of a new p-carboxylated 1,2-bis(diphenylphosphino)benzene ligand are effectively utilized as tetratopic building blocks to prepare isostructural porous coordination polymers with accessible reactive metal sites (M = Pd, Pt). The crystalline materials exhibit unusual and fully reversible H2 sorption at 150 °C. Post-synthetic reactivity is also possible, in which Pt-Cl bonds can be activated to provide organometallic species in the pores.
The new porous phosphine coordination material, PCM-11, is an unusual 8,4-connected coordination polymer with an open 3-D pore structure, formed by reaction of Mg(II) with tris(para-carboxylato)triphenylphosphine oxide. The highly ionic nature of the metal-ligand bonding results in excellent thermal stability upon desolvation (>460 °C). PCM-11 is easily activated for small molecule sorption at low temperature without the requirement for solvent pre-exchange. It adsorbs 47.5 wt% CO(2) at 11.6 bar and 30 °C.
The tetrahedral zwitterion of tetrakis(p-carboxyphenyl) phosphonium is employed as a unique building block for robust and lighter MOFs that tolerate sorption of acidic gases including H2S.
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