Tetravalent Terbium Chelates: Stability Enhancement and Property Tuning

Tianjiao Xue1,2; You-Song Ding1,2; Xue-Lian Jiang1,2; Lizhi Tao1; Jun Li1,2,3; Zhiping Zheng1,2

2023-10-02

10.1021/prechem.3c00065

Precision Chemistry   影响因子和分区

2771-9316

Coordination chemistry of rare-earth elements has been dominated by the +3 oxidation state. Complexes with higher-valence lanthanide ions are synthetically challenging but are of fundamental research interest and significance as advanced molecular materials. Herein, four tetravalent terbium complexes (2-5) of the common formula [Tb(OSiPh3)(4)L] (L = ethylene glycol dimethyl ether (DME), 2,2(')-bipyridine (bpy), 2,2(')-bipyrimidine (bpym), and 1,10-phenanthroline (phen)) are reported. Crystallographic analyses reveal in each of these complexes a hexacoordinate Tb(IV) ion situated in a distorted octahedral coordination environment formed by four triphenylsiloxido ligands and a bidentate chelating ligand. The use of chelating ligands enhances the stability of the resulting complexes over their THF solvate precursor. More significantly, the aromatic N-chelating ligands have been found to tune effectively the electronic structures of the complexes, as evidenced by the sizable potential shifts observed for the quasi-reversible redox Tb(IV/III) process and by the changes in their absorption spectra. The experimental findings are augmented with quantum theoretical calculations in which the ligand pi-donation to the 5d orbitals of the Tb(IV) center is found to be primarily responsible for stability enhancement and the corresponding changes of physical properties observed. Magnetic measurements and results from electron paramagnetic resonance studies produced small absolute values of zero-field splittings of these complexes, ranging from 0.1071(22) to 1.1484(112) cm(-1) and comparable to the values reported for analogous Tb(IV) complexes.

Tetravalent Terbium Ion Chelating Ligand Formal Potential Stability Magnetic Property

ESCI

英语

第一 ; 通讯

National Natural Science Foundation of China["92261203","22101116","22033005","21971106"] ; Key Laboratory of Rare Earth Chemistry of Guangdong Higher Education Institutes[2022KSYS006] ; Stable Support Plan Program of Shenzhen Natural Science Fund[20200925161141006] ; Shenzhen Fundamental Research Program[JCYJ20220530115001002] ; Postdoctoral Scientific Research Fund[K21217520] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:001283160100001

AMER CHEMICAL SOC

人工提交

正式出版

1.Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China
2.Key University Laboratory of Rare Earth Chemistry of Guangdong, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China
3.Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Tsinghua University, Beijing 100084, China

Tianjiao Xue,You-Song Ding,Xue-Lian Jiang,et al. Tetravalent Terbium Chelates: Stability Enhancement and Property Tuning[J]. Precision Chemistry,2023,1(10):583–591.

Tianjiao Xue,You-Song Ding,Xue-Lian Jiang,Lizhi Tao,Jun Li,&Zhiping Zheng.(2023).Tetravalent Terbium Chelates: Stability Enhancement and Property Tuning.Precision Chemistry,1(10),583–591.

Tianjiao Xue,et al."Tetravalent Terbium Chelates: Stability Enhancement and Property Tuning".Precision Chemistry 1.10(2023):583–591.