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.

An ew Mg II -based version of the porous coordination polymer CUK-1 with one-dimensional pore structure was prepared by microwave synthesis in water.M g-CUK-1 is moisture-stable,t hermally stable up to 500 8 8C, and shows unusual reversible soft-crystal behavior:d ehydrated single crystals of the material selectively adsorb ar ange of organic molecules at ambient temperature and pressure.B oth polar and apolar aromatic compounds,including pyridine,benzene, p-xylene,a nd 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 DVBd emonstrate ah igh and rapid selective adsorption of p-DVB and exclusion of m-DVB and ethylvinylbenzene isomers.A number of porous coordination polymers (PCPs) have been shown to possess the ability to effectively separate complex mixtures of gases [1] and, less commonly,o fl iquid hydrocarbons.[2] Thel atter represents at angible application for such materials,e specially to achieve separations that cannot be easily performed using common large-scale separation methods (e.g., column chromatography,ion exchange, fractional distillation). [3,4] One such example concerns the separation of isomers of divinylbenzene (DVB): p-DVBi s important in the manufacture of cross-linked styrene polymers,w hich, paradoxically,a re utilized in the manufacturing of ion-exchange resins.[4] DVBi sp repared by dehydrogenation of crude mixtures of o-, m-, and p-diethylbenzene. Commercially available DVBconsists of approximately 80 % m-and p-DVB along with the products of partial dehydrogenation, m-and p-ethylvinylbenzene (EVB). From an industrial standpoint, pure p-DVB is most preferred for the formation of ordered cross-linked styrene/p-DVB copolymers,but largescale separation approaches have proven to be inefficient. [5] In 2007, we published the discovery of ah ighly porous cobalt(II)-based coordination polymer named CUK-1, which has received significant attention because of its exceptional ability to separate complex gas mixtures.[6] CUK-1 is based on 2,4-pyridinedicarboxylic acid (2,4-pdc) and contains onedimensional channels with square pore windows.The material was shown to be highly robust, owing to the presence of infinite one-dimensional metal hydroxide chains that support ac orrugated wall structure.O ne potential drawback of transition-metal-based materials is the potential for slow hydrolytic decomposition. Ongoing efforts to determine methods for the preparation of more highly stable phases of CUK-1 using alternative metals have ultimately yielded afast, reproducible,and high-yielding method for the production of aM g II analogue.M g-CUK-1 is conveniently prepared in water with ar apid and energy-efficient microwave(mw)-assisted method that yields ac rystalline product in only 35 min at 200 8 8C. Replacement of CoII with Mg II was our ultimate goal, ...

Two new isostructural phosphine coordination materials, Ln-PCM-21 (Ln = Pr, Nd), have been obtained using a tris(p-carboxylated) methyltriphenylphosphonium ligand that is formally dianionic when triply deprotonated, allowing access to materials based on uncommon metal-to-ligand ratios. The polymers of the formula [Ln3(mptbc)4]X·solv (X = Cl(-), NO3(-)) are cationic and contain unusual, linear oxo-bridged [Ln3](9+) clusters. Magnetic susceptibility data for both the Pr and Nd analogues has been compared to models based on three contrasting approaches.