Complex isomerism influencing the textural properties of organometallic [Cu(salen)] porous polymers: paramagnetic solid-state NMR characterization and heterogeneous catalysis.

Although organometallic porous polymer networks are recognized as promising heterogeneous catalysts, the relationship between ligand/monomer geometry and network parameters is usually not well understood due to the lack of atom-resolved characterization methods for the amorphous network matrix. In this work, a series of copper(II) salen-type metal complexes was synthesized, using - and -1,2-diaminocyclohexane segments, and thoroughly characterized by single-crystal X-ray diffraction and solution- and solid-state NMR spectroscopy. Terminal ethynyl groups of the complexes were then transformed into polyacetylene chains by coordination chain-growth homopolymerization, resulting in highly porous (458-655 m g) organometallic polymer networks with a copper(II) ion content of about 12 wt%.

Combining Polymerization and Templating toward Hyper-Cross-Linked Poly(propargyl aldehyde)s and Poly(propargyl alcohol)s for Reversible HO and CO Capture and Construction of Porous Chiral Networks.

Two series of hyper-cross-linked microporous polyacetylene networks containing either -[CH=C(CH=O)]- or -[CH=C(CHOH)]- monomeric units are reported. Networks are prepared by chain-growth copolymerization of acetal-protected propargyl aldehyde and acetal-protected propargyl alcohol with a 1,3,5-triethynylbenzene cross-linker followed by hydrolytic deprotection/detemplating. Deprotection not only liberates reactive CH=O and CHOH groups in the networks but also modifies the texture of the networks towards higher microporosity and higher specific surface area.

Microporous Hyper-Cross-Linked Polymers with High and Tuneable Content of Pyridine Units: Synthesis and Application for Reversible Sorption of Water and Carbon Dioxide.

New hyper-cross-linked porous organic polymers (POPs) with a high content of pyridine segments (7.86 mmol pyridine g ), and a micro/mesoporous texture are reported. The networks are achieved by the chain-growth homopolymerization of 2,6- and 3,5-diethynylpyridines.

Conformation in Ultrathin Polymer Brush Coatings Resolved by Infrared Nanoscopy.

Polymer brush coatings are effective in preventing blood coagulation or bacterial attachment, but their chain conformation, while vital for this effect, was never characterized in high spatial resolution. Here, we report mid-infrared spectroscopic nanoscopy studies of few-nanometer-thin poly(ethylene oxide) (PEO) films which reveal marked spectral variations along the surface at a length scale smaller than 100 nm and originating only from the physical conformation of the chains. The conformation and average orientation of the polymer chains in the layer is extracted from the spectra with the aid of theoretic modeling, confirming the spontaneous formation of a crystalline phase.