Combining Polymerization and Templating toward Hyper-Cross-Linked Poly(propargyl aldehyde)s and Poly(propargyl alcohol)s for Reversible H 2 O and CO 2 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(CH 2 OH)]- 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 CH 2 OH groups in the networks but also modifies the texture of the networks towards higher microporosity and higher specific surface area. The final networks with CH=O and CH 2 OH groups attached directly to the polyene main chains of the networks have a specific surface area from 400 to 800 m 2 /g and contain functional groups in a high amount, up to 9.6 mmol/g. The CH=O and CH 2 OH groups in the networks serve as active centres for the reversible capture of CO 2 and water vapour. The water vapour capture capacities of the networks (up to 445 mg/g at 297 K) are among the highest values reported for porous polymers, making these materials promising for cyclic water harvesting from the air. Covalent modification of the networks with ( R )-(+)-3-aminopyrrolidine and ( S )-(+)-2-methylbutyric acid enables the preparation of porous chiral networks and shows networks with CH=O and CH 2 OH groups as reactive supports suitable for the anchoring of various functional molecules.