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

Seira Shintoyo, Keishiro Murakami, Takeshi Fujinami, Naohide Matsumoto, Naotaka Mochida, Takayuki Ishida, Yukinari Sunatsuki, Masayuki Watanabe, Masanobu Tsuchimoto, Jerzy Mrozinski, Cecilia Coletti, Nazzareno Re

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Abstract

Terbium(III) and dysprosium(III) complexes with a tripodal N7 ligand containing three imidazoles (H3L) and a bidentate acetate ion (OAc-), [LnIII(H3L)(OAc)](ClO4)2·MeOH·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, gJ = 3/2, 7F6) and the DyIII ion (4f9, J = 15/2, S = 5/2, L = 5, gJ = 4/3, 6H15/2). The Stark splittings of the ground states 7F6 of the TbIII ion and 6H15/2 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-f transitions, and the fine structures assignable to the 5D47F6 transition for 1 and the 6F9/26H15/2 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.

Original languageEnglish
Pages (from-to)10359-10369
Number of pages11
JournalInorganic Chemistry
Volume53
Issue number19
DOIs
Publication statusPublished - Oct 6 2014

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Dysprosium
Terbium
tripods
dysprosium
terbium
Luminescence
Ground state
crystal field theory
acetates
Acetates
Ions
luminescence
Ligands
Crystals
ligands
ground state
ions
imidazoles
diagrams
SIM

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Medicine(all)

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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. / Shintoyo, Seira; Murakami, Keishiro; Fujinami, Takeshi; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Watanabe, Masayuki; Tsuchimoto, Masanobu; Mrozinski, Jerzy; Coletti, Cecilia; Re, Nazzareno.

In: Inorganic Chemistry, Vol. 53, No. 19, 06.10.2014, p. 10359-10369.

Research output: Contribution to journalArticle

Shintoyo, S, Murakami, K, Fujinami, T, Matsumoto, N, Mochida, N, Ishida, T, Sunatsuki, Y, Watanabe, M, Tsuchimoto, M, Mrozinski, J, Coletti, C & Re, N 2014, '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', Inorganic Chemistry, vol. 53, no. 19, pp. 10359-10369. https://doi.org/10.1021/ic501453h
Shintoyo, Seira ; Murakami, Keishiro ; Fujinami, Takeshi ; Matsumoto, Naohide ; Mochida, Naotaka ; Ishida, Takayuki ; Sunatsuki, Yukinari ; Watanabe, Masayuki ; Tsuchimoto, Masanobu ; Mrozinski, Jerzy ; Coletti, Cecilia ; Re, Nazzareno. / 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. In: Inorganic Chemistry. 2014 ; Vol. 53, No. 19. pp. 10359-10369.
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title = "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",
abstract = "Terbium(III) and dysprosium(III) complexes with a tripodal N7 ligand containing three imidazoles (H3L) and a bidentate acetate ion (OAc-), [LnIII(H3L)(OAc)](ClO4)2·MeOH·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, gJ = 3/2, 7F6) and the DyIII ion (4f9, J = 15/2, S = 5/2, L = 5, gJ = 4/3, 6H15/2). The Stark splittings of the ground states 7F6 of the TbIII ion and 6H15/2 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-f transitions, and the fine structures assignable to the 5D4 → 7F6 transition for 1 and the 6F9/2 → 6H15/2 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.",
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T1 - 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

AU - Shintoyo, Seira

AU - Murakami, Keishiro

AU - Fujinami, Takeshi

AU - Matsumoto, Naohide

AU - Mochida, Naotaka

AU - Ishida, Takayuki

AU - Sunatsuki, Yukinari

AU - Watanabe, Masayuki

AU - Tsuchimoto, Masanobu

AU - Mrozinski, Jerzy

AU - Coletti, Cecilia

AU - Re, Nazzareno

PY - 2014/10/6

Y1 - 2014/10/6

N2 - Terbium(III) and dysprosium(III) complexes with a tripodal N7 ligand containing three imidazoles (H3L) and a bidentate acetate ion (OAc-), [LnIII(H3L)(OAc)](ClO4)2·MeOH·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, gJ = 3/2, 7F6) and the DyIII ion (4f9, J = 15/2, S = 5/2, L = 5, gJ = 4/3, 6H15/2). The Stark splittings of the ground states 7F6 of the TbIII ion and 6H15/2 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-f transitions, and the fine structures assignable to the 5D4 → 7F6 transition for 1 and the 6F9/2 → 6H15/2 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.

AB - Terbium(III) and dysprosium(III) complexes with a tripodal N7 ligand containing three imidazoles (H3L) and a bidentate acetate ion (OAc-), [LnIII(H3L)(OAc)](ClO4)2·MeOH·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, gJ = 3/2, 7F6) and the DyIII ion (4f9, J = 15/2, S = 5/2, L = 5, gJ = 4/3, 6H15/2). The Stark splittings of the ground states 7F6 of the TbIII ion and 6H15/2 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-f transitions, and the fine structures assignable to the 5D4 → 7F6 transition for 1 and the 6F9/2 → 6H15/2 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.

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