Network topology diversification of porous organic salts.

Hydrogen-bonded organic frameworks (HOFs) are porous organic materials constructed hydrogen bonds. HOFs have solubility in specific high-polar organic solvents. Therefore, HOFs can be returned to their components and can be reconstructed, which indicates their high recyclability. Network topologies, which are the frameworks of porous structures, control the pore sizes and shapes of HOFs. Therefore, they strongly affect the functions of porous materials. However, hydrogen bonds are usually weak interactions, and the design of the intended network topology in HOFs from their components has been challenging. Porous organic salts (POSs) are an important class of HOFs, are hierarchically constructed strong charge-assisted hydrogen bonds between sulfonic acids and amines, and therefore are expected to have high designability of the porous structure. However, the network topology of POSs has been limited to only -topology. Here, we combined tetrasulfonic acid with the adamantane core (4,4',4'',4'''-(adamantane-1,3,5,7-tetrayl)tetrabenzenesulfonic acid; AdPS) and triphenylmethylamines with modified substituents in -positions of benzene rings (TPMA-X, X = F, methyl (Me), Cl, Br, I). We changed the steric hindrance between the adamantane and substituents (X) in TPMA-X and obtained not only the common -topology for POSs but also rare -topology, and - and -topologies that are formed for the first time in HOFs. Changing template molecules under preparation helped in successfully isolating the porous structures of AdPS/TPMA-Me with -, -, and -topologies which exhibited different gas adsorption properties. Therefore, for the first time, we demonstrated that the steric design of HOF components facilitated the formation, diversification, and control of the network topologies and functions of HOFs.