Chinese Version
Home | About Journal | Editorial Board | Information for Authors | Copyright Transfer Statement | Contact us
Interaction Behavior Between Hexa-dentate Polypyrrolic Macrocycles and Actinyl Species: Bonding, Thermodynamic and Spectroscopic Properties
Author NameAffiliationE-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
Chinese Journal of Inorganic Chemistry