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. The pyridine segments form links interconnecting the polyacetylene main chains in these networks. The content of pyridine segments in the networks can be tuned by copolymerizing diethynylpyridines with 1,3-diethynylbenzene. The pyridine rings in the networks serve as base and hydrophilic centers for the sorption of CO and water. The homopolymer pyridine networks are highly efficient in the low-pressure adsorption/desorption of CO . This sorption mode is promising for the postcombustion removal of CO from the fuel gas. The poly(3,5-diethynylpyridine) network exhibits high efficiency in capturing and releasing water vapor (determined capacity 376 mg g at 298 K and relative humidity (RH) = 90% is one of the highest values reported for POPs) and is a promising material for the cyclic water harvesting from air. The reported networks are characterized by C cross-polarization magic angle spinning NMR, thermogravimetric analysis, and N adsorption/desorption and their efficiency in CO and H O capturing is discussed in relation to the content and type of incorporated pyridine segments.