Enantiomeric Separation on a Homochiral Porous Organic Cage-Based Chiral Stationary Phase by Gas Chromatography

摘要

Porous organic cages (POCs) are an emerging class of porous molecular materials which self-assembled by discrete, shape-persistent, cage-like molecules and have recently received intensive interest in diverse fields. In this work, a hydroxyl-functionalized homochiral POC was synthesized by [4 + 6] condensation of 2-hydroxy-1,3,5-triformylbenzene with (1R, 2R)-diaminocyclohexane and coated on a capillary column for gas chromatography (GC) separations. Forty-one pairs of enantiomers belonging to various classes have been resolved on the column, including alcohols, diols, esters, lactones, halohydrocarbons, ethers, epoxides, ketones and sulfoxides. Compared with beta-cyclodextrin derivative-based commercial beta-DEX 120 column, previously reported chiral POCs- (CC9 and CC10) based columns, there are 12, 27 and 19 pairs of studied enantiomers cannot be resolved on beta-DEX 120 column, CC9 column and CC10 column, respectively. Besides, both separation factors and resolution values of some racemates are higher on this column than those on beta-DEX 120 column, CC9 column and CC10 column. The results demonstrate that the column exhibits good chiral recognition complementarity or superior chiral resolution capability to those columns which used for comparison, and the introduction of hydroxyl group enhances hydrogen-bonding interaction to some racemates, leading to better enantioselectivity. The column also shows excellent separation performance toward positional isomers of dichlorobenzene, dibromobenzene, nitrotoluene, chlorotoluene, nitrobromobenzene and nitrochlorobenzene. The retention time and selectivity of analytes have no significant changes after more than 500 injections and 260 degrees C conditioned for 6 h, showing the good repeatability and thermal stability of the column. This work indicates the promising prospect of POCs for GC separation, especially for the separation of enantiomers and also demonstrates the significance of design and synthesis of more functionalized chiral POCs for GC enantioseparation that broaden the enantiomer separation scope and applicability of POCs-based columns through their chiral recognition complementarities.