Synthesis and structures of fluoride-bridged dysprosium clusters: influence of fluoride ions on magnetic relaxation behaviors. Issue 10 (13th April 2022)

• Record Type: Journal Article
• Authors: Yuan, Qiong; Meng, Yin-Shan; Zhang, Yi-Quan; Gao, Chen; Liu, Shan-Shan; Wang, Bing-Wu; Gao, Song
• Is Part Of: Inorganic chemistry frontiers. Volume 9:Issue 10(2022)
• Page Start: 2336
• Page End: 2342
• Publication Date: 2022-04-13
• Subjects: Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d1qi01422f
• Languages: English
• ISSNs: 2052-1553

Abstract

Abstract : The synthesis of fluoride-bridged 1Dy, 2Dy and hepta-nuclear 3Dy dysprosium complexes is reported here and a hydroxy-bridged dinuclear dysprosium complex 4Dy is synthesized for comparison. Abstract : The synthesis of fluoride-bridged tri-([{Cp′2 Dy}{μ-F}]3 ·tol, 1Dy, Cp′ = C5 H4 Si(CH3 )3 ; tol = toluene), tetra-([{Cp′2 Dy(μ-F)2 }2 {(Cp′)(THF)Dy(μ-F)}2 ]·hex, 2Dy, THF = tetrahydrofuran; hex = n -hexane), and hepta-nuclear (3Dy ) dysprosium complexes is reported here and a hydroxy-bridged dinuclear dysprosium complex [Cp′2 Dy(μ-OH)]2 (4Dy ) is synthesized for comparison. The nucleation number of the fluoride-bridged complexes highly depends on the reaction solvents and the molar ratio of the dysprosium and fluoride precursors. The three Dy ions in 1Dy are arranged in a triangular fashion and the tetranuclear 2Dy displays a butterfly shape geometry. 3Dy shows a much more complicated structure with three types of fluoride bridges. 1Dy and 2Dy exhibit slow relaxation of magnetization with the energy barriers of 95 K and 98 K, respectively, while the dinuclear and heptanuclear dysprosium complexes barely show any behaviors of molecular nanomagnets. Ab initio calculations demonstrated that the thermo-assisted relaxation of magnetization of 1Dy and 2Dy originated from the {Cp′2 Dy} fragment. Analysis of magneto-structural correlation revealed that the fluoride ions had a great influence on the orientation of the easy axis of magnetization and the exchange interactions.