Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged ZnII2LnIII2 complexes [(μ4-CO3)2{ZnIIL N ′-Bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato)

Kiyomi Ehama; Yusuke Ohmichi; Soichiro Sakamoto; Takeshi Fujinami; Naohide Matsumoto; Naotaka Mochida; Takayuki Ishida; Yukinari Sunatsuki; Masanobu Tsuchimoto; Nazzareno Re

doi:10.1021/ic4022273

Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn^II₂Ln^III₂ complexes [(μ₄-CO₃)₂{Zn^IIL N ′-Bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato)

Kiyomi Ehama, Yusuke Ohmichi, Soichiro Sakamoto, Takeshi Fujinami, Naohide Matsumoto, Naotaka Mochida, Takayuki Ishida, Yukinari Sunatsuki, Masanobu Tsuchimoto, Nazzareno Re

Advanced Science Research Center

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Abstract

Carbonato-bridged Zn^II₂Ln^III₂ complexes [(μ₄-CO₃)₂{Zn^IIL ⁿLn^III(NO₃)}₂]·solvent were synthesized through atmospheric CO₂ fixation reaction of [Zn ^IILⁿ(H₂O)₂]·xH₂O, Ln^III(NO₃)₃·6H₂O, and triethylamine, where Ln^III = Gd^III, Tb^III, by a spin Hamiltonian including the crystal field effect on the Ln ^III ions and the Ln^III-Ln^III magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of Zn^II₂Tb^III₂ complexes were observed, while those of Zn^II₂Dy ^III₂ were not detected. The fine structure assignable to the ⁵D₄ → ⁷F₆ transition of ZnTb1 and ZnTb2 is in good accord with the energy pattern from the magnetic analysis. The Zn^II₂Ln^III₂ complexes (Ln^III = Tb^III, Dy^III) showed an out-of-phase signal with frequency-dependence in alternating current susceptibility, indicative of single molecule magnet. Under a dc bias field of 1000 Oe, the signals become significantly more intense and the energy barrier, Δ/k _B, for the magnetic relaxation was estimated from the Arrhenius plot to be 39(1) and 42(8) K for ZnTb1 and ZnTb2, and 52(2) and 67(2) K for ZnDy1 and ZnDy2, respectively.

Original language	English
Pages (from-to)	12828-12841
Number of pages	14
Journal	Inorganic Chemistry
Volume	52
Issue number	21
DOIs	https://doi.org/10.1021/ic4022273
Publication status	Published - Nov 4 2013

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic4022273

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Ehama, K., Ohmichi, Y., Sakamoto, S., Fujinami, T., Matsumoto, N., Mochida, N., Ishida, T., Sunatsuki, Y., Tsuchimoto, M., & Re, N. (2013). Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn^II₂Ln^III₂ complexes [(μ₄-CO₃)₂{Zn^IIL N ′-Bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato). Inorganic Chemistry, 52(21), 12828-12841. https://doi.org/10.1021/ic4022273

Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn^II₂Ln^III₂ complexes [(μ₄-CO₃)₂{Zn^IIL N ′-Bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato). / Ehama, Kiyomi; Ohmichi, Yusuke; Sakamoto, Soichiro et al.
In: Inorganic Chemistry, Vol. 52, No. 21, 04.11.2013, p. 12828-12841.

Research output: Contribution to journal › Article › peer-review

Ehama, K, Ohmichi, Y, Sakamoto, S, Fujinami, T, Matsumoto, N, Mochida, N, Ishida, T, Sunatsuki, Y, Tsuchimoto, M & Re, N 2013, 'Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn^II₂Ln^III₂ complexes [(μ₄-CO₃)₂{Zn^IIL N ′-Bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato)', Inorganic Chemistry, vol. 52, no. 21, pp. 12828-12841. https://doi.org/10.1021/ic4022273

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title = "Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged ZnII2LnIII2 complexes [(μ4-CO3)2{ZnIIL N ′-Bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato)",

abstract = "Carbonato-bridged ZnII2LnIII2 complexes [(μ4-CO3)2{ZnIIL nLnIII(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn IILn(H2O)2]·xH2O, LnIII(NO3)3·6H2O, and triethylamine, where LnIII = GdIII, TbIII, by a spin Hamiltonian including the crystal field effect on the Ln III ions and the LnIII-LnIII magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of ZnII2TbIII2 complexes were observed, while those of ZnII2Dy III2 were not detected. The fine structure assignable to the 5D4 → 7F6 transition of ZnTb1 and ZnTb2 is in good accord with the energy pattern from the magnetic analysis. The ZnII2LnIII2 complexes (LnIII = TbIII, DyIII) showed an out-of-phase signal with frequency-dependence in alternating current susceptibility, indicative of single molecule magnet. Under a dc bias field of 1000 Oe, the signals become significantly more intense and the energy barrier, Δ/k B, for the magnetic relaxation was estimated from the Arrhenius plot to be 39(1) and 42(8) K for ZnTb1 and ZnTb2, and 52(2) and 67(2) K for ZnDy1 and ZnDy2, respectively.",

author = "Kiyomi Ehama and Yusuke Ohmichi and Soichiro Sakamoto and Takeshi Fujinami and Naohide Matsumoto and Naotaka Mochida and Takayuki Ishida and Yukinari Sunatsuki and Masanobu Tsuchimoto and Nazzareno Re",

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doi = "10.1021/ic4022273",

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T1 - Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged ZnII2LnIII2 complexes [(μ4-CO3)2{ZnIIL N ′-Bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato)

AU - Ehama, Kiyomi

AU - Ohmichi, Yusuke

AU - Sakamoto, Soichiro

AU - Fujinami, Takeshi

AU - Matsumoto, Naohide

AU - Mochida, Naotaka

AU - Ishida, Takayuki

AU - Sunatsuki, Yukinari

AU - Tsuchimoto, Masanobu

AU - Re, Nazzareno

PY - 2013/11/4

Y1 - 2013/11/4

N2 - Carbonato-bridged ZnII2LnIII2 complexes [(μ4-CO3)2{ZnIIL nLnIII(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn IILn(H2O)2]·xH2O, LnIII(NO3)3·6H2O, and triethylamine, where LnIII = GdIII, TbIII, by a spin Hamiltonian including the crystal field effect on the Ln III ions and the LnIII-LnIII magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of ZnII2TbIII2 complexes were observed, while those of ZnII2Dy III2 were not detected. The fine structure assignable to the 5D4 → 7F6 transition of ZnTb1 and ZnTb2 is in good accord with the energy pattern from the magnetic analysis. The ZnII2LnIII2 complexes (LnIII = TbIII, DyIII) showed an out-of-phase signal with frequency-dependence in alternating current susceptibility, indicative of single molecule magnet. Under a dc bias field of 1000 Oe, the signals become significantly more intense and the energy barrier, Δ/k B, for the magnetic relaxation was estimated from the Arrhenius plot to be 39(1) and 42(8) K for ZnTb1 and ZnTb2, and 52(2) and 67(2) K for ZnDy1 and ZnDy2, respectively.

AB - Carbonato-bridged ZnII2LnIII2 complexes [(μ4-CO3)2{ZnIIL nLnIII(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn IILn(H2O)2]·xH2O, LnIII(NO3)3·6H2O, and triethylamine, where LnIII = GdIII, TbIII, by a spin Hamiltonian including the crystal field effect on the Ln III ions and the LnIII-LnIII magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of ZnII2TbIII2 complexes were observed, while those of ZnII2Dy III2 were not detected. The fine structure assignable to the 5D4 → 7F6 transition of ZnTb1 and ZnTb2 is in good accord with the energy pattern from the magnetic analysis. The ZnII2LnIII2 complexes (LnIII = TbIII, DyIII) showed an out-of-phase signal with frequency-dependence in alternating current susceptibility, indicative of single molecule magnet. Under a dc bias field of 1000 Oe, the signals become significantly more intense and the energy barrier, Δ/k B, for the magnetic relaxation was estimated from the Arrhenius plot to be 39(1) and 42(8) K for ZnTb1 and ZnTb2, and 52(2) and 67(2) K for ZnDy1 and ZnDy2, respectively.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn^II₂Ln^III₂ complexes [(μ₄-CO₃)₂{Zn^IIL N ′-Bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato)

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