Tetravalent Terbium Chelates: Stability Enhancement and Property Tuning
作者机构：Department of ChemistrySouthern University of Science and TechnologyShenzhenGuangdong 518055China Key University Laboratory of Rare Earth Chemistry of GuangdongSouthern University of Science and TechnologyShenzhenGuangdong 518055China Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of EducationTsinghua UniversityBeijing 100084China
出 版 物：《Precision Chemistry》 (精准化学（英文）)
年 卷 期：2023年第1卷第10期
页 面：583-591页
学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学]
基 金：supported by the National Natural Science Foundation of China(92261203,22101116,22033005 and 21971106) Key Laboratory of Rare Earth Chemistry of Guangdong Higher Education Institutes(2022KSYS006) the Stable Support Plan Program of Shenzhen Natural Science Fund(20200925161141006),Shenzhen Fundamental Research Program(JCYJ20220530115001002) Postdoctoral Scientific Research Fund for staying at(coming to)Shenzhen(K21217520) The calculations were performed with SUSTech supercomputer and were supported by Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)
主 题：Tetravalent Terbium Ion Chelating Ligand Formal Potential Stability Magnetic Property
摘 要：Coordination chemistry of rare-earth elements has been dominated by the+3 oxidation *** with higher-valence lanthanide ions are synthetically challenging but are of fundamental research interest and significance as advanced molecular ***,four tetravalent terbium complexes(2-5)of the common formula[Tb(OSiPh3)4L](L=ethylene glycol dimethyl ether(DME),2,2’-bipyridine(bpy),2,2’-bipyrimidine(bpym),and 1,10-phenanthroline(phen))are *** analyses reveal in each of these complexes a hexacoordinate Tb(IV)ion situated in a distorted octahedral coordination environment formed by four triphenylsi-loxido ligands and a bidentate chelating *** use of chelating ligands enhances the stability of the resulting complexes over their THF solvate *** 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 *** experimental findings are augmented with quantum theoretical calculations in which the ligandπ-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 *** 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.
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