|
Interaction Behavior Between Hexa-dentate Polypyrrolic Macrocycles and Actinyl Species: Bonding, Thermodynamic and Spectroscopic Properties |
Author Name | Affiliation | E-mail | BI Yan-Ting | Science and Technology Division, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China | | YAO Jun | Science and Technology Division, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China | | SHEN Zhong-Hui | Science and Technology Division, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China | shenzhonghui@hlju.edu.cn | ZHANG Hong-Xing | Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China | | PAN Qing-Jiang | Science and Technology Division, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China | panqjitc@163.com |
|
Abstract: A relativistic density functional theory (DFT) was used to systematically examine a series of uranyl and transuranyl complexes of N-donor macrocyclic ligands,[(AnO2)(Ln)]2-(labeled as nAn; n=1~3; An=U, Np and Pu). Further comparison was made with[(UO2)(L0)]2-(A) that was experimentally synthesized. Cavities of L1 and L2 macrocycles are found to match well with actinyl ions, but the one of L3 is a lot larger. Consequently, the L3 complexes have to adopt distorted geometry to energetically stabilize systems. Infrared vibrational spectra presented that the An=O stretching frequencies decrease in going from U, Np to Pu. This agrees with the trend of optimized bond lengths of An=O and bond orders. Topological analyses of quantum theory of atoms in molecule (QTAIM) indicate that the An-N bonds have largely ionic character. Depending on different actinyl source, free energies reacting with various macrocyclic ligands were calculated around 146.4 kJ·mol-1, comparable to the calculated values of A. Time-dependent DFT calculations on four uranyl complexes well reproduced absorption spectra of experimentally reported analogue. The absorption bands in the near-IR and visible region have large contribution from ligand-to-metal charge transfer (LMCT), which is responsible for changes of solution color in the process of macrocyclic ligand sensing uranyl species. |
Keywords: polypyrrollic uranyl/transuranyl complexes QTAIM analysis thermodynamic reaction electronic spectroscopy relativistic DFT |
Hits: 1100 |
Download times: 618 |
BI Yan-Ting,YAO Jun,SHEN Zhong-Hui,ZHANG Hong-Xing,PAN Qing-Jiang.Interaction Behavior Between Hexa-dentate Polypyrrolic Macrocycles and Actinyl Species: Bonding, Thermodynamic and Spectroscopic Properties[J].Chinese Journal of Inorganic Chemistry,2018,34(6):1071-1078. |
View Full Text View/Add Comment Download reader |
|
|
|
|
|