Theory Investigation Of Nonsymmetrically Substituted Uranyl-salophen Complexes And The Model Of Them Coordinated With Cyclohexenone

The absolute configuration structure and spectral properties of the nonsymmetrically substituted uranyl-salophen complexes were rarely reported, because uranyl-salophen were instable and hard to be separated with high purity. By studying the geometry structures, spectral quality and molecular orbitals of the uranyl-salophen, we are able to get their absolute configuration. Theoretical investigation of the chiral molecular recognition of the nonsymmetrically substituted uranyl-salophens could provide theoretical guidance for experiment. By simulate the structure of nonsymmetrically substituted uranyl-salophen coordinated with cyclohexenone, it could deepen the recognition to the molecular recognition of the nonsymmetrically substituted uranyl-salophe. Coupled with the inherent chirality of the nonsymmetrically substituted uranyl-salophen, the complexes offered new appealing opportunities for their applications. Theoretical investigation of the chiral molecular recognition of the nonsymmetrically substituted uranyl-salophens could provide theoretical guidance for experiment. From the following several aspects the article states the research content and methods, analyses and get the related conclusion.Chapter one:In this chapter the introduction, research background research background and significance of this topic was in included. Among them the introduction of the intermolecular forces 、Schiff base、uranyl ion 、 uranyl-salophen and advances in nonsymmetrically substituted uranyl-salophens was given out.Chapter two: In this chapter the introduction of Gaussian 09 software and the development history of the density functional theory(DFT) were involved.Chapter three: In this chapter, the absolutely structure of the nonsymmetrically substituted uranyl-salophen complexes were studed. The structures, spectral properties and molecular orbitals of six nonsymmetrically substituted uranyl-salophen complexes were investigated. Phenolic hydroxyl groups were able to form hydrogen bonds with the N atoms in the ligands, which played a great impact both on IR and NMR spectra. For an absolute configuration of "?", a positive absorption peak emerged first, then a negative absorption peak followed in the ECD spectra of uranyl-salophen within the range of 250-500 nm. This chapter thus provided a theoretical basis and guidance for the design and synthesis of uranyl-salophen with desirable functions.Chapter foure: In this chapter, we calculated the three nonsymmetrically substituted uranyl-salophen coordinated with cyclohexenone. Then their geometries, IR spectrum, thermodynamic properties, electronic structures were discussed. The molecular orbital of the complexes which uranyl-salophen coordinating with cyclohexenone were also be taken into consideration. The results showed that the U atom of Uranyl-Salophen coordinated with the oxygen atom of cyclohexenone reduced the conjugation effects of C=C and C=O in cyclohexenone and the aranyl complexes are more stable. The cyclohexenone was located in the inside of the cleft of the uranyl-salophens in the complexes. With the increasing of the aromatic substituent in the asymmetrical uranyl-salophens, the binding energy between the uranyl-salophens and the carbonyl compounds could be increased. The aromatic walls provided van der Waals interactions to the guest which played an important role in reaction when the asymmetrical uranyl-salophens act as catalyst. All thepreliminary results threw light on the chiral catalytic ability of the asymmetrical uranyl-salophens.Chapter five: In this chapter, we summarized the whole paper.