Synthesis And Characterization Of The Metal Phosphates With Chiral Characterization

Chiral molecular sieves attract considerable attention, because of theirextensive application in enantioselective catalysis, separation and pharmacy.There have been three general methodologies that have been employed forobtaining chiral molecular sieves. One is to modify an existing inorganicmaterial with a chiral organic component through either intercalation orsurface anchoring. The second is to incorporate chiral moieties into thebuilding blocks of an organic-inorganic hybrid framework constructed throughcoordination of the organic component to the metal cations. The thirdapproach is to impart chirality to an as-synthesized inorganic open-frameworkby using a chiral template. The first two approaches have been remarkablysuccessful. For example, by using chirally modified zeolites as catalysts,stereoselective photoreactions have been achieved; therefore, racemicmixtures of small organic molecules have been resolved using materialsobtained by the second approach. However, the third approach to chiralmolecular sieves, in spite of some remarkable effort, has led to few successes.Optically pure chiral zeolitic material has never been made. The lack of success to impart chirality from a template to a molecularsieve is perhaps due to, firstly, a lack of understanding of the interactionsbetween a template and a corresponding framework. Furthermore, it may not 136具有手性结构特征的金属磷酸盐的合成与表征 吉林大学博士学位论文have been appreciated that, in order for transfer of chirality to occur, multipointcooperative non-covalent interactions stronger than van der waals forces areperhaps necessary. As a starting point for understanding the role of a chiraltemplate in determining the stereospecificity of an inorganic frameworkstructure, we have chosen to focus on the role of hydrogen bonding, becauseit has been suggested to play a role in inducing chirality in analuminophosphate with a chiral template, and multiple hydrogen bonds areknown to cooperatively exert dramatic influences on the supramolecularassemblies in chemical and biological system. In this thesis, we first system analysize the syntheses, structures of metalphosphates with chiral characterization, and the intraction between thetemplate and the inorganic host framework. over ten new chiral metalophosphates, vanadium borophosphate compounds and vanadium oxideshave been successfully prepared. There are JLU-1; JLU-2; JLU-3； JLU-4；JLU-5; JLU-6；JLU-7；JLU-8; JLU-9；JLU-10；JLU-11. in addition, we havepreparated a novel zinc phosphate-phosphite ZnPO-CJ12 and zincphosphate ZnPO-CJ16。 [Co(en)3][Zn8P6O24Cl]·2H2O (JLU-1) is the first 3-D zinc phosphatecompound by using the metal complex Co(en)3Cl3 as the template. Theframework structure of JLU-1 built up of ZnO4, ZnO3Cl, and PO4 tetrahedracan be viewed as stacking of the zinc phosphate layers along the c axis linkedby Cl atoms as pillars to generate interesting tunnels with 12-MR windows.The structure JLU-1 contain chiral structural motifs. The enantiomers ofCo(en)3 3+ are separated as ? and Λ configurations in the structures of JLU-1and interact with the inorganic hosts through H-bonding interactions. [CoII(en)3]2·[Zn6P8O32H8] (JLU-2) consists of vertex-linking ZnO4 andPO3(OH) tetrahedral units forming macroanionic sheets with 4.6.8-nets. Thestructure JLU-2 contain chiral structural motifs. The enantiomers of Co(en)3 3+are separated as ? and Λ configurations in the structures of JLU-2 and 137具有手性结构特征的金属磷酸盐的合成与表征 吉林大学博士学位论文interact with the inorganic hosts through H-bonding interactions. [CoII(en)3][Zn4(H2PO4)3(HPO4)2(PO4)(H2O)2] (JLU-3) reveals that theracemic cobalt complex templates the zinc phosphate framework in such away that the local C2 point symmetry of the structural motif of t...