Citation: Zhong-Xue LONG, Wei LI, Dong-Fang LI, Jia-Hui JING, Shan-Shan LIU. Synthesis, crystal structure, luminescence, and density functional theory calculation of rare earth complexes based on 1-phenyl-3-methyl-4-benzoyl-5-pyrazolinone[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(3): 385-394. doi: 10.11862/CJIC.2023.009 shu

Synthesis, crystal structure, luminescence, and density functional theory calculation of rare earth complexes based on 1-phenyl-3-methyl-4-benzoyl-5-pyrazolinone

Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology, College of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China

Corresponding author: Shan-Shan LIU, liushanshan2015@bipt.edu.cn
Received Date: 5 July 2022
Revised Date: 20 December 2022

Figures(7)

A series of mononuclear rare earth complexes [Ln(pmbp)₃(dmbipy)]·C₂H₅OH, where Ln=Tb (1-Tb), Ho (1-Ho), Er (1-Er) and Tm (1-Tm), were synthesized by using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolinone (Hpmbp) and 4,4'-dimethyl-2,2'-bipyridine (dmbipy) as ligands. Structure characterizations show that the complex is composed of one Ln³⁺ ion, three pmbp^-ions, one dmbipy molecule, and one free ethanol molecule, yielding the [LnO₆N₂] type structure. The continuous shape measurement (CShM) analyses show that the Ln³⁺ centers exhibit a distorted triangular dodecahedral geometry. Luminescence measurements showed that all of the complexes exhibit characteristic emission peaks of the corresponding rare earth ions. And it was found that the ligand could sensitize Ho³⁺ and Er³⁺ well, while the sensitization of Tb³⁺ and Tm³⁺ was weak. In addition, the HOMO and LUMO of Hpmbp ligands, dmbipy ligands, and rare earth complexes were calculated and analyzed by the density functional theory method. It is found that for Tb, Ho, and Tm complexes with an odd number of electrons in the center metal atom, the bond lengths between metal ions and coordination atoms are shorter with the increasing number of electrons in metal ions, while the bond lengths of Er—O and Er—N of 1-Er are between those of 1-Ho and 1-Tm. For 1-Tb, 1-Ho, and 1-Tm, the orbital energy of HOMO and LUMO decreases with increasing electron number, which is consistent with the rule of bond length. For 1-Tb, 1-Ho and 1-Er, the HOMO-LUMO gap increases with the increase of electron number. In addition, the HOMO-LUMO energy gaps of the four complexes are lower than that of the ligands.
- 1-phenyl-3-methyl-4-benzoyl-5-pyrazolinone,
- rare earth complex,
- luminescence,
- density functional theory calculation
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