Ami Takahiro, Oka Kouki, Tsuchiya Keiho, Tohnai Norimitsu
Department of Applied Chemistry and Center for Future Innovation (CFi), Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.
Angew Chem Int Ed Engl. 2022 Aug 1;61(31):e202202597. doi: 10.1002/anie.202202597. Epub 2022 May 19.
Porous organic salts (POSs) are porous organic materials, in which various aromatic sulfonic acids and amines are regularly self-assembled by charge-assisted hydrogen bonding. POSs exhibit high solubility in highly polar solvents. Therefore, they are prepared via facile recrystallization and exhibit high recyclability. In this study, tetrahedral-structured tetrasulfonic acid and triphenylmethylamine (TPMA) were combined to construct POSs with rigid diamond networks called diamondoid porous organic salts (d-POSs). Furthermore, by introducing substituents (e.g., F, Cl, Br, or I) at the para-positions of benzene rings of TPMA, these substituents were exposed on the void surface of d-POSs, and their diamond networks were distorted. This induced the formation of a variety of void structures and environments in the d-POSs, which significantly affected their gas adsorption behavior. In particular, the d-POS from TPMA substituted by fluorine exhibited very high CO adsorption of 182 mL(STP) g at 1 atm in all-organic porous materials.
多孔有机盐（POSs）是多孔有机材料，其中各种芳族磺酸和胺通过电荷辅助氢键规则地自组装。POSs在高极性溶剂中表现出高溶解度。因此，它们通过简便的重结晶制备并表现出高可回收性。在本研究中，将四面体结构的四磺酸与三苯甲基胺（TPMA）结合，构建具有刚性金刚石网络的POSs，称为类金刚石多孔有机盐（d-POSs）。此外，通过在TPMA苯环的对位引入取代基（例如F、Cl、Br或I），这些取代基暴露在d-POSs的孔隙表面上，并且它们的金刚石网络发生扭曲。这导致在d-POSs中形成各种孔隙结构和环境，这显著影响了它们的气体吸附行为。特别地，在所有有机多孔材料中，由氟取代的TPMA形成的d-POS在1个大气压下对CO的吸附量非常高，为182 mL(STP) g 。
