Spirobifluorene‐Based Porous Organic Salts: Their Porous Network Diversification and Construction of Chiral Helical Luminescent Structures

Porous organic salts (POSs) are organic porous materials assembled via charge‐assisted hydrogen bonds between strong acids and bases such as sulfonic acids and amines. To diversify the network topology of POSs and extend its functions, this study focused on using 4,4′,4′′,4′′′‐(9,9′‐spirobi[fluorene]‐2,2′,7,7′‐tetrayl)tetrabenzenesulfonic acid (spiroBPS), which is a tetrasulfonic acid comprising a square planar skeleton. The POS consisting of spiroBPS and triphenylmethylamine (TPMA) (spiroBPS/TPMA) was constructed from the two‐fold interpenetration of an orthogonal network with pts topology, which has not been reported in conventional POSs, owing to the shape of the spirobifluorene backbone. Furthermore, combining tris(4‐chlorophenyl)methylamine (TPMA‐Cl) and tris(4‐bromophenyl)methylamine (TPMA‐Br), which are bulkier than TPMA owing to the introduction of halogens at the p‐position of the phenyl groups with spiroBPS allows us to construct novel POSs (spiroBPS/TPMA‐Cl and spiroBPS/TPMA‐Br). These POSs were constructed from a chiral helical network with pth topology, which was induced by the steric hindrance between the halogens and the curved fluorene skeleton. Moreover, spiroBPS/TPMA‐Cl with pth topology exhibited circularly polarized luminescence (CPL) in the solid state, which has not been reported in hydrogen‐bonded organic frameworks (HOFs). Porous organic salts (POSs) with a chiral helical network were constructed from a square‐planar sulfonic acid and p‐position‐modified triphenylmethylamine, both achiral components. The chirality of the POSs could be controlled by chiral induction, and the obtained porous materials composed of hydrogen bonds exhibited solid‐state circularly polarized luminescence (CPL). This study highlights applications for POSs as chiral materials.