基于乳酸衍生物的螺旋手性配位聚合物的合成与荧光性质

Helical Homochiral Coordination Polymers Based on Semirigid Lactic Derivatives:Syntheses and Fluorescence Properites

在水热条件下,半刚性的乳酸衍生物(R)-(1-羧基乙氧基)苯甲酸[(R)-H2CBA]和(S)-(1-羧基乙氧基)苯甲酸[(S)-H2CBA]分别与辅助配体1,1′-(2,5-二甲基-1,4-亚苯基)双(1H-咪唑),1,4-PBM和Zn(Ⅱ)反应,合成了一对包含螺旋链的三维超分子手性配位聚合物[Zn2((R)-CBA)2(1,4-PBM)2]n(1-D,CCDC:2010329)和[Zn2((S)-CBA)2(1,4-PBM)2]n(1-L,CCDC:2010330),其结构和性能经IR,XRD,TGA和FL表征。结果表明:1-D结晶于单斜的P21手性空间群,晶胞参数a=8.9753(5)Å,b=18.2446(8)Å,c=15.1201(12)Å,β=90.935(6)°,V=2475.7(3)Å3,Dc=1.373 g·cm-3,Z=2,Flack parameter=0.022(6);作为对映体,1-L也结晶于单斜的P21手性空间群,晶胞参数a=9.0090(6)Å,b=18.2280(8)Å,c=15.1227(10)Å,β=90.935(6)°,V=2483.1(3)Å3,Dc=1.369 g·cm-3,Z=2,Flack parameter=0.060(7)。1-D和1-L的初始分解温度为317℃;1-D在440 nm处有强发射峰。

Under hydrothermal conditions,two homochiral coordination polymers,namely[Zn2((R)-CBA)2(1,4-PBM)2]n(1-D,CCDC:2010329)and[Zn2((S)-CBA)2(1,4-PBM)2]n(1-L,CCDC:2010330),were synthesized by Zn(Ⅱ),auxiliary ligand 1,1′-(2,5-dimethyl-1,4-phenylene)bis(1H-imidazole),semirigid lactic derivatives(R)-4-(1-carboxyethoxy)benzoic acid or(S)-4-(1-carboxyethoxy)benzoic acid,respectively.The single crystal X-ray diffraction data have revealed that complexes 1-D and 1-L are 3D supramolecular frameworks with unique helical chain.Among them,complex 1-D crystallized in the monoclinic crystal system and chiral P21 space group with a=8.9753(5)Å,b=18.2446(8)Å,c=15.1201(12)Å,β=90.935(6)°,V=2475.7(3)Å3,Dc=1.373 g·cm-3,Z=2 and Flack parameter=0.022(6).As enantiomer,complex 1-L also crystallized in the monoclinic crystal system and chiral P21 space group with a=9.0090(6)Å,b=18.2280(8)Å,c=15.1227(10)Å,β=90.935(6)°,V=2483.1(3)Å3,Dc=1.369 g·cm-3,Z=2 and Flack parameter=0.060(7).