Volume 43, Issue 2 pp. 131-138
Comprehensive Report

Exploring the Magnetism of C5/C2B3 Heteroleptic Organolanthanide Sandwiches

Ye-Ye Liu

Ye-Ye Liu

Frontier Institute of Science and Technology (FIST), State Key Laboratory of Electrical Insulation and Power Equipment, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Xi’an Key Laboratory of Electronic Devices and Material Chemistry and School of Chemistry, Xi’an Jiaotong University, Xi’an, Shaanxi, 710054 China

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Qian-Cheng Luo

Qian-Cheng Luo

Frontier Institute of Science and Technology (FIST), State Key Laboratory of Electrical Insulation and Power Equipment, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Xi’an Key Laboratory of Electronic Devices and Material Chemistry and School of Chemistry, Xi’an Jiaotong University, Xi’an, Shaanxi, 710054 China

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Peng-Bo Jin

Corresponding Author

Peng-Bo Jin

Frontier Institute of Science and Technology (FIST), State Key Laboratory of Electrical Insulation and Power Equipment, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Xi’an Key Laboratory of Electronic Devices and Material Chemistry and School of Chemistry, Xi’an Jiaotong University, Xi’an, Shaanxi, 710054 China

E-mail: [email protected]; [email protected]Search for more papers by this author
Yan-Zhen Zheng

Corresponding Author

Yan-Zhen Zheng

Frontier Institute of Science and Technology (FIST), State Key Laboratory of Electrical Insulation and Power Equipment, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Xi’an Key Laboratory of Electronic Devices and Material Chemistry and School of Chemistry, Xi’an Jiaotong University, Xi’an, Shaanxi, 710054 China

Department of Hepatobiliary Surgery and Institute of Advanced Surgical Technology and Engineering, The First Affiliated Hospital of Xi’an Jiaotong University, Xi’an, Shaanxi, 710061 China

E-mail: [email protected]; [email protected]Search for more papers by this author
First published: 07 October 2024

Comprehensive Summary

Two families of cyclopentadienyl (Cp)/carboranyl heteroleptic sandwiched organolanthanide complexes, namely [Ln{η5:σ-Me2C(C5H4)(C2B10H10)}2][Li(DME)3] (1Ln, Ln = Tb, Dy, Ho, Er) and [2-THF-2'-(μ2-Cl)Li(THF)3-2,2'-Ln(nido-1,7-C2B9H11)Cp*] (2Dy), were synthesized. Family of 1Ln has been proposed based on the mixing-ligands idea by linking Cp and nido-dicarborllide. However, the carborane cage of [Me2C(C5H4)(C2B10H10)]2− deprotons and forms a mono-C anion rather than deboron to form dicarborllide dianion. Hence, the family of 1Ln features a dysprosocenium skeleton with extra two coordination of C anions of carborllides. Such coordination geometry is more like a tetrahedron if abstracting the centroids of two coordinated Cp rings. In this cubic-type geometry, no significant magnetic axiality is presented; only 1Dy and 1Tb show field-induced slow magnetic relaxation behavior below 10 K. Inspired by 1Ln, the free pentamethylcyclopentadienyl (Cp*) and nido-dicarborllide ligands are used to sandwich central Dy3+ ion, achieving heteroleptic complex 2Dy. The bending angle by linking the centroid of Cp*, Dy3+ and C2B32− in 2Dy is increased to 132.8(1)°. As such, the effective energy barrier for magnetic reversal (Ueff) and magnetic blocking temperature TB (ZFC) are both increased (Ueff = 616(10) K; TB = 6 K). The effort of further enhancing Ueff and TB in such heteroleptic organolanthanide sandwiches should rely on keeping increasing the ligand axiality.

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