1⁃苯基⁃3⁃甲基⁃4⁃苯甲酰基⁃5⁃吡唑啉酮稀土配合物的合成、晶体结构、发光性能与密度泛函理论计算  

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

作　　者：龙忠学 李巍[1] 李东芳 景佳慧 刘姗姗 LONG Zhong-Xue;LI Wei;LI Dong-Fang;JING Jia-Hui;LIU Shan-Shan(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)

机构地区：[1]北京石油化工学院新材料与化工学院,燃料清洁化及高效催化减排技术北京市重点实验室,北京102617

出　　处：《无机化学学报》2023年第3期385-394,共10页Chinese Journal of Inorganic Chemistry

基　　金：北京市自然科学基金(No.2202016);国家自然科学基金(No.21602013);国家级大学生创新创业计划项目(No.2022J00028)资助。

摘　　要：以1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮(Hpmbp)和4,4′-二甲基-2,2′-联吡啶(dmbipy)为配体合成了一类单核稀土配合物[Ln(pmbp)3(dmbipy)]·C2H_(5)OH,其中Ln=Tb(1⁃Tb)、Ho(1⁃Ho)、Er(1⁃Er)、Tm(1⁃Tm)。结构表征显示该类配合物由稀土金属离子与3个pmbp-配体、1个dmbipy配体配位而成,同时存在一分子非配位的乙醇。Ln^(3+)离子的配位环境均接近于三角十二面体构型。荧光测试表明,1⁃Tb、1⁃Ho、1⁃Er和1⁃Tm均表现出了相应稀土离子的特征发射峰。此外,利用密度泛函理论计算分析了Hpmbp配体、dmbipy配体及稀土配合物的HOMO-LUMO信息。A series of mononuclear rare earth complexes[Ln(pmbp)3(dmbipy)]·C2H_(5)OH,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 Ln^(3+)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 Ln^(3+)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 Tb^(3+)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.CCDC:2181993,1⁃Tb;2181994,1⁃Ho;2181995,1⁃Er;2181996,1⁃Tm.

关 键 词：1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮 稀土配合物 荧光 密度泛函理论计算 

分 类 号：O614.341[理学—无机化学] O614.343[理学—化学] O614.344O614.345