Strong intramolecular ferromagnetic couplings in nickel(II) and copper(II) complexes chelated with tert-butyl 5-methoxy-2-pyridyl nitroxide

Atsushi Okazawa; Takashi Nogami; Takayuki Ishida

doi:10.1016/j.poly.2008.10.049

Strong intramolecular ferromagnetic couplings in nickel(II) and copper(II) complexes chelated with tert-butyl 5-methoxy-2-pyridyl nitroxide

Atsushi Okazawa, Takashi Nogami, Takayuki Ishida^*

^*この研究の対応する著者

研究成果: Article › 査読

23 被引用数 (Scopus)

抄録

We successfully isolated a new paramagnetic bidentate ligand tert-butyl 5-methoxy-2-pyridyl nitroxide (meopyNO). Complexation of nickel(II) and copper(II) perchlorates with meopyNO gave the corresponding ML₂-type bis-chelated compounds. The magnetic studies showed that they were ground high-spin molecules with 2J/k_B = +288(5) and +178(3) K for [M(meopyNO)₂(H₂O)₂] · (ClO₄)₂ (M = Ni and Cu, respectively), where the spin Hamiltonian is defined as H = -2J(S₁ · S₂ + S₂ · S₃). From the crystallographic analysis, the torsion angles (φ{symbol}) around M-O-N-C_2py were 4.2(3)° and 6.87(19)°, respectively, being so small that the orthogonality between the magnetic radical π* and the metal dσ orbitals would be guaranteed.

本文言語	English
ページ（範囲）	1917-1921
ページ数	5
ジャーナル	Polyhedron
巻	28
号	9-10
DOI	https://doi.org/10.1016/j.poly.2008.10.049
出版ステータス	Published - 2009 6月 22
外部発表	はい

ASJC Scopus subject areas

物理化学および理論化学
無機化学
材料化学

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title = "Strong intramolecular ferromagnetic couplings in nickel(II) and copper(II) complexes chelated with tert-butyl 5-methoxy-2-pyridyl nitroxide",

abstract = "We successfully isolated a new paramagnetic bidentate ligand tert-butyl 5-methoxy-2-pyridyl nitroxide (meopyNO). Complexation of nickel(II) and copper(II) perchlorates with meopyNO gave the corresponding ML2-type bis-chelated compounds. The magnetic studies showed that they were ground high-spin molecules with 2J/kB = +288(5) and +178(3) K for [M(meopyNO)2(H2O)2] · (ClO4)2 (M = Ni and Cu, respectively), where the spin Hamiltonian is defined as H = -2J(S1 · S2 + S2 · S3). From the crystallographic analysis, the torsion angles (φ{symbol}) around M-O-N-C2py were 4.2(3)° and 6.87(19)°, respectively, being so small that the orthogonality between the magnetic radical π* and the metal dσ orbitals would be guaranteed.",

keywords = "Aminoxyl, Free radical, High-spin molecule, Magnetic interaction",

author = "Atsushi Okazawa and Takashi Nogami and Takayuki Ishida",

note = "Funding Information: This work was supported by Grants-in-Aid for Scientific Research (Nos. 17550166 and 19550135) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.",

year = "2009",

month = jun,

day = "22",

doi = "10.1016/j.poly.2008.10.049",

language = "English",

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T1 - Strong intramolecular ferromagnetic couplings in nickel(II) and copper(II) complexes chelated with tert-butyl 5-methoxy-2-pyridyl nitroxide

AU - Okazawa, Atsushi

AU - Nogami, Takashi

AU - Ishida, Takayuki

N1 - Funding Information: This work was supported by Grants-in-Aid for Scientific Research (Nos. 17550166 and 19550135) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

PY - 2009/6/22

Y1 - 2009/6/22

N2 - We successfully isolated a new paramagnetic bidentate ligand tert-butyl 5-methoxy-2-pyridyl nitroxide (meopyNO). Complexation of nickel(II) and copper(II) perchlorates with meopyNO gave the corresponding ML2-type bis-chelated compounds. The magnetic studies showed that they were ground high-spin molecules with 2J/kB = +288(5) and +178(3) K for [M(meopyNO)2(H2O)2] · (ClO4)2 (M = Ni and Cu, respectively), where the spin Hamiltonian is defined as H = -2J(S1 · S2 + S2 · S3). From the crystallographic analysis, the torsion angles (φ{symbol}) around M-O-N-C2py were 4.2(3)° and 6.87(19)°, respectively, being so small that the orthogonality between the magnetic radical π* and the metal dσ orbitals would be guaranteed.

AB - We successfully isolated a new paramagnetic bidentate ligand tert-butyl 5-methoxy-2-pyridyl nitroxide (meopyNO). Complexation of nickel(II) and copper(II) perchlorates with meopyNO gave the corresponding ML2-type bis-chelated compounds. The magnetic studies showed that they were ground high-spin molecules with 2J/kB = +288(5) and +178(3) K for [M(meopyNO)2(H2O)2] · (ClO4)2 (M = Ni and Cu, respectively), where the spin Hamiltonian is defined as H = -2J(S1 · S2 + S2 · S3). From the crystallographic analysis, the torsion angles (φ{symbol}) around M-O-N-C2py were 4.2(3)° and 6.87(19)°, respectively, being so small that the orthogonality between the magnetic radical π* and the metal dσ orbitals would be guaranteed.

KW - Aminoxyl

KW - Free radical

KW - High-spin molecule

KW - Magnetic interaction

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