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Quantum Chemistry Study On The Catalytic Activity Of Uranyl-Salophen Complexes

Posted on:2017-02-01Degree:MasterType:Thesis
Country:ChinaCandidate:S GaoFull Text:PDF
GTID:2311330491458237Subject:Applied Chemistry
Abstract/Summary:PDF Full Text Request
It is difficult to get the pure uranyl-salophen by means of the purification method, so some molecular parameters are hard to obtain and some characteristic parameters of the compounds complexing by the uranyl-salophen with some molecules can not be found by the experimental methods. However, the theoretical calculation is a good way to solve those problems. The theoretical calculation can get a lots of molecular parameters of the uranyl-salophen and corresponding complexes, such as the infrared spectrum, the geometric configuration, molecular orbital, electronic data. According to the structure characters of uranyl-salophen, introduced aromatic in the side of the uranyl-salophen, it make the uranyl-salophen have the ability of chiral molecules, so in this paper, based on the theoretical calculation, at the level of molecular, uranyl Salophen derivatives and its complexes has been studied. Based on Density Functional Theory(DFT) calculations, the molecular recognition of uranyl-salophen receptors to ?, ?-unsaturated carbonyl compound guests and chiral molecules were theoretically investigated. The results showed that the U atom of the receptors was coordinated by the O3 atom of the guests, the binding energies between receptors and guests were increased with the enlargement of the aromatic substituent in the uranyl-salophen receptors, the U-O3 coordination bonds of R2-, R3-series complexes have larger stability than R1-series complexes, the conjugation effect between the C=C and C=O of the ?,?-unsaturated carbonyl compounds in coordination complexes was weakened. The molecular recognition selectivity of asymmetrical uranyl-salophen receptor 3 to(R)-1-(2-naphthy) ethylami- ne was much better than to(S)-1-(2-naphthy) ethylamine according to Circular Dichroism(CD) spectra and the binding energy calculations. These results thus threw light on the recognition ability of the asymmetrical uranyl-salophens.Based on density functional theory(DFT) calculation method, the hydrogen bonds formed by the uranyl-salophen with tetrahydropyrrole and water were theoretically calculated and studied. The results showed that the hydrogen bond lengths were less than 2.28?, bond angles were 160 °~178 ° in system 1 and system 2, and the hydrogen bond energy(O1 ··· H1-N3) EHB was-10.658 k J/mol in the system 1. In system 2, hydrogen bond energy between the O3 and the H3, H1 and O1 were-7.989 k J/mol,-11.114 k J/mol, respectively. These results thus threw light on the C-O and U=O of the uranyl-salophen could form hydrogen bonds and the stability of the hydrogen bonding C-O···H-N was better than U=O···H-N.
Keywords/Search Tags:Density functional theory, Uranyl-salophen, ?,?-unsaturated carbonyl compound, Molecular recognition, Hydrogen bond
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