One-, Two-, and Three-Dimensional Heterospin Complexes Consisting of 4-(N-tert-Butyloxylamino)pyridine (4NOpy), Dicyanamide Ion (DCA), and 3d Metal Ions: Crystal Structures and Magnetic Properties of [MII(4NOpy)x(DCA)y(CH3CN)z]n (M = Mn, Co, Ni, Cu, Zn)

Hiraku Ogawa, Koya Mori, Kensuke Murashima, Satoru Karasawa, Noboru Koga

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Abstract

Solutions of 3d metal ion salts, M(NO3)2, 4-(N-tert-butyloxylamino)pyridine (4NOpy), and dicyanamide (DCA) in CH3CN were mixed to afford single crystals of the polymeric complexes [MII(4NOpy)x(DCA)y(CH3CN)z]n (MII = Mn (1), Co (2), Ni (3), Cu (4a and 4b), Zn (5)). X-ray crystallography revealed that the crystal structures are a three-dimensional (3-D) network for 1, 2-D networks for 2, 3, 4a, and 5, and a 1-D chain for 4b. Crystals of 2, 3, 4a, and 5 contained CH3CN molecules as crystal solvents, which were readily desorbed in the ambient atmosphere. After desorption of the CH3CN molecules, the crystal structures of 2 and 3 were confirmed to be slightly shrunk without destruction of the crystal lattice. Crystals of 2, 3, 4a, and 5 after desorption of crystal solvents were used for investigations of the magnetic properties. Complex 1 showed antiferromagnetic interactions to form a ferrimagnetic chain and exhibited the magnetic behavior of a 2-D (or 3-D) spin-canted antiferromagnet with TN = 12 K. Complex 2 containing anisotropic CoII ions also showed the behavior of a 1-D (or 2-D) spin-canted antiferromagnet with TN = 6 K. In 3, 4a, and 4b, the aminoxyl of 4NOpy ferromagnetically interacted with the metal ion with coupling constants of JM-NO/kB = 45, 45, and 43 K, respectively. In 5, the magnetic couplings between the aminoxyls in 4NOpy through the diamagnetic ZnII ion were weakly antiferromagntic (JNO-NO = -1.2 K). DCA might be a weak antiferromagnetic connector for the metal chains.

Original languageEnglish
Pages (from-to)717-728
Number of pages12
JournalInorganic chemistry
Volume55
Issue number2
DOIs
Publication statusPublished - Jan 19 2016

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Metal ions
metal ions
pyridines
Magnetic properties
Crystal structure
Ions
magnetic properties
Crystals
crystal structure
crystals
Desorption
ions
desorption
Magnetic couplings
Molecules
X ray crystallography
connectors
crystal lattices
Crystal lattices
crystallography

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{5897b08604214fc0b072f938f4ff2c71,
title = "One-, Two-, and Three-Dimensional Heterospin Complexes Consisting of 4-(N-tert-Butyloxylamino)pyridine (4NOpy), Dicyanamide Ion (DCA), and 3d Metal Ions: Crystal Structures and Magnetic Properties of [MII(4NOpy)x(DCA)y(CH3CN)z]n (M = Mn, Co, Ni, Cu, Zn)",
abstract = "Solutions of 3d metal ion salts, M(NO3)2, 4-(N-tert-butyloxylamino)pyridine (4NOpy), and dicyanamide (DCA) in CH3CN were mixed to afford single crystals of the polymeric complexes [MII(4NOpy)x(DCA)y(CH3CN)z]n (MII = Mn (1), Co (2), Ni (3), Cu (4a and 4b), Zn (5)). X-ray crystallography revealed that the crystal structures are a three-dimensional (3-D) network for 1, 2-D networks for 2, 3, 4a, and 5, and a 1-D chain for 4b. Crystals of 2, 3, 4a, and 5 contained CH3CN molecules as crystal solvents, which were readily desorbed in the ambient atmosphere. After desorption of the CH3CN molecules, the crystal structures of 2 and 3 were confirmed to be slightly shrunk without destruction of the crystal lattice. Crystals of 2, 3, 4a, and 5 after desorption of crystal solvents were used for investigations of the magnetic properties. Complex 1 showed antiferromagnetic interactions to form a ferrimagnetic chain and exhibited the magnetic behavior of a 2-D (or 3-D) spin-canted antiferromagnet with TN = 12 K. Complex 2 containing anisotropic CoII ions also showed the behavior of a 1-D (or 2-D) spin-canted antiferromagnet with TN = 6 K. In 3, 4a, and 4b, the aminoxyl of 4NOpy ferromagnetically interacted with the metal ion with coupling constants of JM-NO/kB = 45, 45, and 43 K, respectively. In 5, the magnetic couplings between the aminoxyls in 4NOpy through the diamagnetic ZnII ion were weakly antiferromagntic (JNO-NO = -1.2 K). DCA might be a weak antiferromagnetic connector for the metal chains.",
author = "Hiraku Ogawa and Koya Mori and Kensuke Murashima and Satoru Karasawa and Noboru Koga",
year = "2016",
month = "1",
day = "19",
doi = "10.1021/acs.inorgchem.5b02159",
language = "English",
volume = "55",
pages = "717--728",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
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TY - JOUR

T1 - One-, Two-, and Three-Dimensional Heterospin Complexes Consisting of 4-(N-tert-Butyloxylamino)pyridine (4NOpy), Dicyanamide Ion (DCA), and 3d Metal Ions

T2 - Crystal Structures and Magnetic Properties of [MII(4NOpy)x(DCA)y(CH3CN)z]n (M = Mn, Co, Ni, Cu, Zn)

AU - Ogawa, Hiraku

AU - Mori, Koya

AU - Murashima, Kensuke

AU - Karasawa, Satoru

AU - Koga, Noboru

PY - 2016/1/19

Y1 - 2016/1/19

N2 - Solutions of 3d metal ion salts, M(NO3)2, 4-(N-tert-butyloxylamino)pyridine (4NOpy), and dicyanamide (DCA) in CH3CN were mixed to afford single crystals of the polymeric complexes [MII(4NOpy)x(DCA)y(CH3CN)z]n (MII = Mn (1), Co (2), Ni (3), Cu (4a and 4b), Zn (5)). X-ray crystallography revealed that the crystal structures are a three-dimensional (3-D) network for 1, 2-D networks for 2, 3, 4a, and 5, and a 1-D chain for 4b. Crystals of 2, 3, 4a, and 5 contained CH3CN molecules as crystal solvents, which were readily desorbed in the ambient atmosphere. After desorption of the CH3CN molecules, the crystal structures of 2 and 3 were confirmed to be slightly shrunk without destruction of the crystal lattice. Crystals of 2, 3, 4a, and 5 after desorption of crystal solvents were used for investigations of the magnetic properties. Complex 1 showed antiferromagnetic interactions to form a ferrimagnetic chain and exhibited the magnetic behavior of a 2-D (or 3-D) spin-canted antiferromagnet with TN = 12 K. Complex 2 containing anisotropic CoII ions also showed the behavior of a 1-D (or 2-D) spin-canted antiferromagnet with TN = 6 K. In 3, 4a, and 4b, the aminoxyl of 4NOpy ferromagnetically interacted with the metal ion with coupling constants of JM-NO/kB = 45, 45, and 43 K, respectively. In 5, the magnetic couplings between the aminoxyls in 4NOpy through the diamagnetic ZnII ion were weakly antiferromagntic (JNO-NO = -1.2 K). DCA might be a weak antiferromagnetic connector for the metal chains.

AB - Solutions of 3d metal ion salts, M(NO3)2, 4-(N-tert-butyloxylamino)pyridine (4NOpy), and dicyanamide (DCA) in CH3CN were mixed to afford single crystals of the polymeric complexes [MII(4NOpy)x(DCA)y(CH3CN)z]n (MII = Mn (1), Co (2), Ni (3), Cu (4a and 4b), Zn (5)). X-ray crystallography revealed that the crystal structures are a three-dimensional (3-D) network for 1, 2-D networks for 2, 3, 4a, and 5, and a 1-D chain for 4b. Crystals of 2, 3, 4a, and 5 contained CH3CN molecules as crystal solvents, which were readily desorbed in the ambient atmosphere. After desorption of the CH3CN molecules, the crystal structures of 2 and 3 were confirmed to be slightly shrunk without destruction of the crystal lattice. Crystals of 2, 3, 4a, and 5 after desorption of crystal solvents were used for investigations of the magnetic properties. Complex 1 showed antiferromagnetic interactions to form a ferrimagnetic chain and exhibited the magnetic behavior of a 2-D (or 3-D) spin-canted antiferromagnet with TN = 12 K. Complex 2 containing anisotropic CoII ions also showed the behavior of a 1-D (or 2-D) spin-canted antiferromagnet with TN = 6 K. In 3, 4a, and 4b, the aminoxyl of 4NOpy ferromagnetically interacted with the metal ion with coupling constants of JM-NO/kB = 45, 45, and 43 K, respectively. In 5, the magnetic couplings between the aminoxyls in 4NOpy through the diamagnetic ZnII ion were weakly antiferromagntic (JNO-NO = -1.2 K). DCA might be a weak antiferromagnetic connector for the metal chains.

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U2 - 10.1021/acs.inorgchem.5b02159

DO - 10.1021/acs.inorgchem.5b02159

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JF - Inorganic Chemistry

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