Crystal Field Splitting of the Ground State of Terbium(III) and Dysprosium(III) Complexes with a Triimidazolyl Tripod Ligand and an Acetate Determined by Magnetic Analysis and Luminescence

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• 作者：Seira Shintoyo ; Keishiro Murakami ; Takeshi Fujinami ; Naohide Matsumoto ; Naotaka Mochida ; Takayuki Ishida ; Yukinari Sunatsuki ; Masayuki Watanabe ; Masanobu Tsuchimoto ; Jerzy Mrozinski ; Cecilia Coletti ; Nazzareno Re
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：October 6, 2014
• 年：2014
• 卷：53
• 期：19
• 页码：10359-10369
• 全文大小：593K
• ISSN：1520-510X

文摘

Terbium(III) and dysprosium(III) complexes with a tripodal N₇ ligand containing three imidazoles (H₃L) and a bidentate acetate ion (OAc^{鈥?/sup>), [LnIII(H₃L)(OAc)](ClO₄)₂路MeOH路H₂O (Ln = Tb, 1; Ln = Dy, 2), were synthesized and studied, where H₃L = tris[2-(((imidazol-4-yl)methylidene)amino)ethyl]amine. The TbIII and DyIII complexes have an isomorphous structure, and each TbIII or DyIII ion is coordinated by the tripodal N₇ and the bidentate acetate ligands, resulting in a nonacoordinated capped-square-antiprismatic geometry. The magnetic data, including temperature dependence of the magnetic susceptibilities and field dependence of the magnetization, were analyzed by a spin Hamiltonian, including the crystal field effect on the TbIII ion (4f8, J = 6, S = 3, L = 3, g_J = 3/2, 7F₆) and the DyIII ion (4f9, J = 15/2, S = 5/2, L = 5, g_J = 4/3, 6H_15/2). The Stark splittings of the ground states 7F₆ of the TbIII ion and 6H_15/2 of the DyIII ion were evaluated from the magnetic analyses, and the energy diagram patterns indicated an easy axis (Ising type) anisotropy for both complexes, which is more pronounced for 2. The solid-state emission spectra of both complexes displayed sharp bands corresponding to the f鈥揻 transitions, and the fine structures assignable to the 5D₄ 鈫?7F₆ transition for 1 and the 6F_9/2 鈫?6H_15/2 transition for 2 were related to the energy diagram patterns from the magnetic analyses. 1 and 2 showed an out-of-phase signal with frequency dependence in alternating current (ac) susceptibility under a dc bias field of 1000 Oe, indicative of a field-induced SIM.}