Study On Chiral Metallacycles And Chiral Porous Organic Cages Used As Stationary Phases For Gas Chromatography

Gas chromatography（GC）is an important chiral separation and analysis method.It is also of great significance to develop novel chiral stationary phases（CSPs）with high separation efficiency,good enantioselectivity,simple preparation and good stability for GC.Metallacycles are a class of supramolecular complexes,which directly constructed by self-assembly of metal ions with organic ligands.Porous organic cages（POCs）are an emerging class of porous molecular materials,which are self-assembled by discrete,shape-persistent,three-dimensional cage-like molecules through weak intermolecular forces.Both metallacycles and POCs have unique intrinsic cavities which can accommodate guest molecules and occur rich host-guest interactions.They have important application prospects in the fields of supramolecular chemistry and molecular recognition and separation.Metallacycles and POCs also have good solubility that easy to solution-processing.As stationary phases,it is also convenient to prepare capillary GC columns using static coating method.In this thesis,two chiral metallacycles and one chiral POC were synthesized and used as CSPs to prepare.capillary GC columns by static coating method.The separation performance of the fabricated columns toward chiral compounds,isomers,and organic mixtures were investigated.The specific research works are as follows:（1）In introduction,the definition of chirality,the significance of chiral separation and chiral separation methods were first introduced.Secondly,GC,the classification of CSPs of GC and the preparation process of capillary GC columns are summarized;Finally,the main synthesis methods and applications of POCs and metallacycles were briefly summarized.（2）A rhombic Zn（II）chiral metallacycle[Zn Cl₂L]₂was synthesized by[2+2]self-assembly of（S）-（1-isonicotinoylpyrrolidin-2-yl）methyl isonicotinate（L）with Zn Cl₂.It was then used as a CSP to prepare capillary column.The separation of chiral compounds,isomers（including structure,positional,cis/trans isomers）,n-alkanes,n-alcohols,aromatic hydrocarbons and Grob mixtures on this column was studied.The experimental results showed that 16 racemates and 21 isomers were obtained different degrees of separation.At the same time,the chiral resolution performance of the column was compared with that ofβ-DEX 120 column.The column can separate some racemates which cannot be separated byβ-DEX 120 column and have good application prospects.（3）A[4+6]-type chiral POC was successfully synthesized by Schiff-base condensationof（S）-（-）-1,1′-binaphthyl-2,2′-diaminewith2,4,6-triformylphloroglucinol.It was used as a stationary phase to prepare chiral POC capillary GC column,and its separation performance for organic isomers and racemates were investigated.A total of 13 racemates and 19 organic isomers were separated on the column.In addition,n-alkanes,n-alcohols,aromatic hydrocarbons and Grob mixtures have also achieved good separation on this column.（4）A[3+3]-type chiral polyimide macrocycle（H₃L）was synthesized and self-assembled with Zn（CH₃COO）₂·2H₂O by coordination to obtain a chiral metallacycle Zn₃L₂.It was used as a stationary phase for GC to prepare a Zn₃L₂based capillary column.The separation performance of the Zn₃L₂capillary column was evaluated using racemates,organic isomers,n-alkanes,n-alcohols and aromatic hydrocarbons as probes.There are 18 racemic compounds and 12 isomers have been separated,and other analytes have also achieved good separation on the column.At the same time,the resolution of racemates on the Zn₃L₂based capillary column was compared with commercialβ-DEX 120 column,showing that the fabricated column had certain advantages in the resolution of some racemates.This result indicates that this chiral metallacycle has certain potential as a stationary phase for GC.