Nitrogen-bonded copper(II)-imino nitroxide complexes exhibiting large ferromagnetic interactions

Luneau, Dominique; Rey, P.; Laugier, J; Fries, Pascal; Caneschi, Andrea; Gatteschi, Dante; Sessoli, Roberta

doi:10.1021/ja00004a026

Cited by 159 publications

(93 citation statements)

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“…The structures of complexes 1a, 1b, 2a, and 2b were determined by X-ray crystallography at 103 or 123 K. All the 9 electron configuration like the Cu II ion, the octahedral geometry does not remain perfect at equilibrium and is inevitably distorted along one axis (the Jahn-Teller effect). [18] A similar deviation from the ideal square geometry is also observed in 1b [Zn-N2 = 2.101(1), Zn-N3 = 2.144(1) Å; N2-Zn-N3 = 85.24(5)°].…”

Section: Crystal Structuresmentioning

confidence: 99%

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Structural and Magnetic Studies of Copper(II) and Zinc(II) Coordination Complexes Containing Nitroxide Radicals as Chelating Ligands

et al. 2006

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The mononuclear transition metal complexes [Cu(CF 3 CN (2b) have been prepared from the newly synthesized doxyl nitroxide ligands 4,4-dimethyl-2,2-di(2-pyridyl)oxazolidine-N-oxyl (1) and 4,4-dimethyl-2,2-bis[2-(3-methylpyridyl)]oxazolidine-N-oxyl (2) and M(CF 3 SO 3 ) 2 (M = Cu II or Zn II ). These metal-nitroxide complexes have been structurally and magnetically characterized. In all complexes, the four pyridyl groups coordinate in equatorial coordination sites and the two nitroxide groups in axial coordination sites, which means that the central metal ion acquires a distorted N 4 O 2 octahedral configuration. The variable-temperature magnetic susceptibility data show

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Section: Crystal Structuresmentioning

confidence: 99%

“…[3] Actually, the dimensionality is restricted due to the prior occupation of coordination sites by the electron-withdrawing coligands. [8,9] Two strategies have been developed to overcome this difficulty. One approach is to use a high-spin poly-(nitroxide radical) as a polydentate bridging ligand to connect the paramagnetic metal ions.…”

Section: Introductionmentioning

confidence: 99%

Structural and Magnetic Studies of Copper(II) and Zinc(II) Coordination Complexes Containing Nitroxide Radicals as Chelating Ligands

et al. 2006

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“…In many different types of organic radicals, research has focused on the nitronyl nitroxide radicals (NITR) family because of their flexibility and functionality [2,3]. Several investigations on the magnetic properties of the nitronyl nitroxide and imino nitroxide radicals of metal complexes have been reported [4][5][6][7][8]. …”

Section: Discussionmentioning

confidence: 99%

Crystal structure of diaquabis{2-[2'-(1'-methylbenzimidazolyl)]-4,4,5,5- tetramethylimidazoline-1-oxyl-3-oxide}mangan(II) bisperchlorate dihydrate, [Mn(H2O)2(C15H19N4O2)2](ClO4)2 · 2H2O

He¹,

Wang²,

Yang³

et al. 2010

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialThe nitroxide 2-{2'-[(1'-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (NIT-1'-MeBzIm) was prepared by the literature method [1]. The methanol solution of NIT-1'-MeBzIm (10 ml, 0.4 mmol) was added dropwise to the methanol solution of Mn(ClO 4 ) 2 · 6H 2 O(15 ml, 0.2 mmol), the mixture was stirred further two hours affording ac olor change from dark purple to dark cyan, then the reaction mixture was filtered. The filtrate was kept in an atmosphere of ether vapor at room temperature. Slow diffusion of ether into the methanol solution of the complex produced cyan single crystals. DiscussionThe design and synthesis of molecule-based magnetic materials are one of the major subjects of materials science. In many different types of organic radicals, research has focused on the nitronyl nitroxide radicals (NITR) family because of their flexibility and functionality [2,3]. Several investigations on the magnetic prop- 2+ are connected to a2 D layer by the intermolecular hydrogen bonds.

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“…The design and synthesis of transition metal complexes with organic free radicals is one of the major challenges in the field of molecular magnetic materials [2,3]. Nitronyl nitroxide radicals (NITR), stable organic radicals, have been widely employed as molecular units in the design and synthesis of molecular magnetic materials [4,5].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of diazido-tetra(2-(4-pyridyl)4,4,5,5-tetramethyl-imidazoline- 1-oxyl-3-oxide)copper(II), Cu(N3)2(C12H16N3O2)4

Yang¹,

Chang²,

Zhao³

2010

Zeitschrift Für Kristallographie - New Crystal Structures

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C 48H64CuN18O8,t riclinic, P1 (no. 2), a =7.133(1) Å, b =13.718(2) Å, c =14.136(2) Å, a =88.425(2)°, b =78.528(2)°, g =87.390(2)°, V =1354.0 Å 3 , Z =1, R gt (F) O(0.200 g, 1mmol) and NITpPy (0.468 g, 2 .mmol). The mixture was stirred for 4hand then filtered. The black filtrate was allowed to stand at room temperature. Black crystals suitable for X-ray analysis were obtained after one week. DiscussionThe design and synthesis of transition metal complexes with organic free radicals is one of the major challenges in the field of molecular magnetic materials [2,3]. Nitronyl nitroxide radicals (NITR), stable organic radicals, have been widely employed as molecular units in the design and synthesis of molecular magnetic materials [4,5]. However, because NITRs are poor electrondonor ligands, their coordination ability is limited. Meanwhile, the azide anion is av ersatile ligand that can link to transitionmetal atoms with different coordination modes. Therefore, to proove advantage of the abilities of both nitronyl nitroxide radicals and the azide anions to coordinate transition metals, we synthesized the metal-radical complex [Cu(NITpPy) 4(N3)2].In the title crystal structure, the metal ion lies on an inversion center and adopts adistorted octahedral environment. It is bonded to four nitrogen atoms of the pyridyl groups in addition to two azido ligands. The two Natoms of the azide groups and the two Natoms of the radical ligands occupy the equatorial positions. The Cu-N bond lengths are 1.993 (2)

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Nitrogen-bonded copper(II)-imino nitroxide complexes exhibiting large ferromagnetic interactions

Cited by 159 publications

References 1 publication

Structural and Magnetic Studies of Copper(II) and Zinc(II) Coordination Complexes Containing Nitroxide Radicals as Chelating Ligands

Structural and Magnetic Studies of Copper(II) and Zinc(II) Coordination Complexes Containing Nitroxide Radicals as Chelating Ligands

Crystal structure of diaquabis{2-[2'-(1'-methylbenzimidazolyl)]-4,4,5,5- tetramethylimidazoline-1-oxyl-3-oxide}mangan(II) bisperchlorate dihydrate, [Mn(H2O)2(C15H19N4O2)2](ClO4)2 · 2H2O

Crystal structure of diazido-tetra(2-(4-pyridyl)4,4,5,5-tetramethyl-imidazoline- 1-oxyl-3-oxide)copper(II), Cu(N3)2(C12H16N3O2)4

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