4f/5d Hybridization Induced Single-Electron Delocalization in an Azide-Bridged Dicerium Complex

Guo, Yan1,2; Jiang, Xue-Lian3,4; Wu, Qun-Yan1; Liu, Kang1; Wang, Wenyuan6; Hu, Kong-qiu1; Mei, Lei1; Chai, Zhi-fang1; Gibson, John K.5; Yu, Ji-pan1; Li, Jun7,8,9; Shi, Wei-qun1

2024-03-04

10.1021/jacs.4c01047

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

Dilanthanide complexes with one-electron delocalization are important targets for understanding the specific 4f/5d-bonding feature in lanthanide chemistry. Here, we report an isolable azide-bridged dicerium complex 3 [{(Trapen(TMS))Ce}(2)(mu-N-3)]center dot [Trapen = tris (2-aminobenzyl)amine; TMS = SiMe3], which is synthesized by the reaction of tripodal ligand-supported (Trapen(TMS))(CeCl)-Cl-IV complex 2 with NaN3. The structure and bonding nature of 3 are fully characterized by X-ray crystal diffraction analysis, electron paramagnetic resonance (EPR), magnetic measurement, cyclic voltammetry, X-ray absorption spectroscopy, and quantum-theoretical studies. Complex 3 presents a trans-bent central Ce-N-3-Ce unit with a single electron of two mixed-valent Ce atoms. The unique low-temperature (2 K) anisotropic EPR signals [g = 1.135, 2.003, and 3.034] of 3 indicate that its spin density is distributed on the central Ce-N-3-Ce unit with marked electron delocalization. Quantum chemical analyses show strong 4f/5d orbital mixing in the singly occupied molecular orbital of 3, which allows for the unpaired electron to extend throughout the cerium-azide-cerium unit via a multicentered one-electron (Ce-N-3-Ce) interaction. This work extends the family of mixed-valent dilanthanide complexes and provides a paradigm for understanding the bonding motif of ligand-bridged dilanthanide complexes.

SCI ; IC ; EI

英语

其他

National Natural Science Foundation of China["22176191","22266026","22033005"] ; National Natural Science Foundation of China[21925603] ; National Science Fund for Distinguished Young Scholars[2232033] ; Beijing Natural Science Foundation[2022M723148] ; China Postdoctoral Science Foundation[2023AAC03014]

Chemistry

Chemistry, Multidisciplinary

WOS:001179752100001

AMER CHEMICAL SOC

Web of Science

1.Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China
2.Ningxia Univ, Sch Chem & Chem Engn, State Key Lab High Efficiency Utilizat Coal Green, Yinchuan 750021, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
4.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalyt Chem, Shenzhen 518055, Peoples R China
5.Lawrence Berkeley Natl Lab LBNL, Chem Sci Div, Berkeley, CA 94720 USA
6.Northwest Univ, Coll Chem & Mat Sci, Minist Educ, Key Lab Synthet & Nat Funct Mol Chem, Xian 710069, Shaanxi, Peoples R China
7.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
8.Tsinghua Univ, Engn Res Ctr Adv Rare Earth Mat, Minist Educ, Beijing 100084, Peoples R China
9.Chinese Acad Sci, Ganjiang Innovat Acad, Fundamental Sci Ctr Rare Earths, Ganzhou 341000, Peoples R China

Guo, Yan,Jiang, Xue-Lian,Wu, Qun-Yan,et al. 4f/5d Hybridization Induced Single-Electron Delocalization in an Azide-Bridged Dicerium Complex[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024,146(10).

Guo, Yan.,Jiang, Xue-Lian.,Wu, Qun-Yan.,Liu, Kang.,Wang, Wenyuan.,...&Shi, Wei-qun.(2024).4f/5d Hybridization Induced Single-Electron Delocalization in an Azide-Bridged Dicerium Complex.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,146(10).

Guo, Yan,et al."4f/5d Hybridization Induced Single-Electron Delocalization in an Azide-Bridged Dicerium Complex".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146.10(2024).