Synthesis of Type II Porous Liquids from Nonporous Metal–Organic Polyhedra Enhanced by Host–Guest Complexation
Abstract
Abstract The synthesis of Type II porous liquids (PLs) from metal–organic polyhedra, a kind of excellent porous molecular sources, suffers from their strong crystallization tendency induced poor solubility. Herein, we propose a host–guest complexation enhanced dissolution strategy for constructing Type II PLs from MOPs with record‐high concentration. Benefitting from host–guest interactions between pillar[5]arene and n ‐alkyl chains, a Type II PL (P5‐PL) is developed by dissolving apolar n ‐dodecyl‐functionalized metal–organic polyhedra (MOP‐18) in polar liquid pillar[5]arene (P5‐L), exhibiting solubility much higher than all MOP‐based Type II PLs reported to date. MOP‐18, being nonporous in the solid state because of molecular packing‐induced pore blockage, displays permanent molecular porosity when molecularly and randomly dispersed in P5‐L to form P5‐PL, as confirmed by experimental and simulation results. P5‐PL demonstrates excellent CO 2 /N 2 separation capabilities, enabling the fabrication of mixed matrix membrane with superior CO 2 /N 2 selectivity. This strategy can be extended to the fabrication of additional Type II PLs, showing its universality. This synergistic design concept integrating supramolecular chemistry with PLs not only overcomes traditional tedious covalent modification but also enables high compatibility between apolar cage solutes and polar solvents, affording PLs with high porosity, low volatility and viscosity, and programmable tunability.
Article Details
Authors (8)
Zhaocong Zhang
State Key Laboratory of Coordination Chemistry MOE Laboratory of Mesoscopic Chemistry Jiangsu Key Laboratory of Advanced Organic Materials School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 P.R. China
Hailong Ning
Hongjun Liu
Vanderbilt University , , , ,
Jingwen Xing
State Key Laboratory of Coordination Chemistry MOE Laboratory of Mesoscopic Chemistry Jiangsu Key Laboratory of Advanced Organic Materials School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 P.R. China
Libing Qian
School of Nuclear Technology and Chemistry & Biology Hubei Key Laboratory of Radiation Chemistry and Functional Materials Hubei University of Science and Technology Xianning 437100 P.R. China
Zhuoheng Tu
State Key Laboratory of Coordination Chemistry MOE Laboratory of Mesoscopic Chemistry Jiangsu Key Laboratory of Advanced Organic Materials School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 P.R. China
De‐en Jiang
Department of Chemical and Biomolecular Engineering Vanderbilt University Nashville Tennessee USA
Kecheng Jie
State Key Laboratory of Coordination Chemistry MOE Laboratory of Mesoscopic Chemistry Jiangsu Key Laboratory of Advanced Organic Materials School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 P.R. China