A series of novel organic cage compounds 1-4 were successfully synthesized from readily available starting materials in one-pot in decent to excellent yields (46-90%) through a dynamic covalent chemistry approach (imine condensation reaction). Covalently cross-linked cage framework 14 was obtained through the cage-to-framework strategy via the Sonogashira coupling of cage 4 with the 1,4-diethynylbenzene linker molecule. Cage compounds 1-4 and framework 14 exhibited exceptional high ideal selectivity (36/1-138/1) in adsorption of CO(2) over N(2) under the standard temperature and pressure (STP, 20 °C, 1 bar). Gas adsorption studies indicate that the high selectivity is provided not only by the amino group density (mol/g), but also by the intrinsic pore size of the cage structure (distance between the top and bottom panels), which can be tuned by judiciously choosing building blocks of different size. The systematic studies on the structure-property relationship of this novel class of organic cages are reported herein for the first time; they provide critical knowledge on the rational design principle of these cage-based porous materials that have shown great potential in gas separation and carbon capture applications.
© 2011 American Chemical Society