铀酰-Salophen与环己烯酮的作用模式

The Mode of Uranyl-Salophen Coordinating with Cyclohexenone

为研究铀酰-Salophen的一些特殊分子识别与催化性能,在真空和氯仿溶液中,采用密度泛函理论(DFT)中的B3LYP/6—311G^(**)方法,对五种铀酰-Salophen的分子结构进行优化。真空条件下计算它们的振动频率,模拟五种铀酰-Salophen与环己烯酮的作用模式,对配位前后铀酰配合物的几何构型、红外光谱、热力学性质、电子结构及配位后分子的分子轨道进行讨论分析。结果表明环己烯酮的氧原子与铀酰-salophen的铀原子发生配位后改变铀酰-Salophen和环己烯酮的电荷分布,削弱了环已烯酮中C=C与C=O之间的共轭作用,使得整个配合物分子的稳定性加强。

To study the special molecular recognition and catalytic performance of Uranyl-Salophen complexes, an optimal calculation on the molecular structure of five Uranyl-Salophen complexes in vacuum and in chloroform solution was studied, using density functional theory （DFT） methods at B3LYP/6-311G＊＊ level. In vacuum, we calculated their vibration frequencies and simulated the five Uranyl-Salophen coordinating with cyclohexenone. Then their geometries, IR spectrum, thermodynamic properties, and electronic structures were discussed. The molecular orbit of the complexes which Uranyl-Salophen coordinating with cyclohexenone were also taken into consideration. The results showed that the uranium atom of Uranyl-Salophen coordinated with the oxygen atom of cyclohexenone changed both their electronic structures in Uranyl-Salophen and cyclohexenone, reduced the conjugation effects of C=C and C=Oin cyclohexenone and the Uranyl complexes are more stable.