Magnetic and structural properties of dinuclear singly bridged-phenoxido metal(II) complexes.

Salah S. Massoud; Mark Spell; Catherine C. Ledet; Thomas Junk; Radovan Herchel; Roland C. Fischer; Zdenek Travnicek; Franz A. Mautner

doi:10.1039/C4DT03508A

Magnetic and structural properties of dinuclear singly bridged-phenoxido metal(II) complexes.

Salah S. Massoud, Mark Spell, Catherine C. Ledet, Thomas Junk, Radovan Herchel, Roland C. Fischer, Zdenek Travnicek, Franz A. Mautner

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

Abstract

The reaction of a methanolic soln. contg. the bi-compartmental phenolic ligand 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenol (LCl-OH) with MCl2·nH2O in the presence of NH4PF6 or NaClO4 afforded the dinuclear bridged-phenoxido dichlorido-metal(II) complexes [Co2(μ-LClO)(H2O)2Cl2][Co2(μ-LClO)(MeOH)2Cl2](PF6)2 (1), [Ni2(μ-LClO)(MeOH)2Cl2]PF6 (2), [Ni2(μ-LClO)(MeOH)(H2O)Cl2]ClO4·1.25H2O (3), [Cu2(μ-LClO)Cl2]PF6·0.5MeOH (4) and [Zn2(μ-LClO)Cl2]PF6·MeOH (5). The complexes were characterized by elemental microanalyses, cond. measurements, IR and UV-visible spectroscopy, mass spectrometry and single crystal x-ray crystallog. Each M(II) center within the dinuclear complex cations is octahedrally coordinated in complexes 1-3, and five-coordinated distorted square pyramidal in 4 and 5. Magnetic susceptibility measurements at variable temp. of the complexes 1-4 revealed weak to moderate antiferromagnetic coupling with |J| values = 8.38, 39.0, 30.2 and 0.79 cm-1, resp. The results of DFT calcns. correlate well with the exptl. detd. antiferromagnetic coupling and show that the magnetic exchange coupling occurs mainly through the phenoxido bridge M-O-M. Implications of geometry around the central metal ion, M···M distance, M-O-M bond angle and overlapping of magnetic orbitals on the magnetic exchange coupling are discussed. [on SciFinder(R)]

Original language	English
Pages (from-to)	2110-2121
Number of pages	12
Journal	Dalton Transactions
Volume	44
Issue number	5
DOIs	https://doi.org/10.1039/C4DT03508A
Publication status	Published - 2015

Fields of Expertise

Advanced Materials Science

Treatment code (Nähere Zuordnung)

Basic - Fundamental (Grundlagenforschung)

Access to Document

10.1039/C4DT03508A

Cite this

@article{da1960166e614b99968727a7312e9164,

title = "Magnetic and structural properties of dinuclear singly bridged-phenoxido metal(II) complexes.",

abstract = "The reaction of a methanolic soln. contg. the bi-compartmental phenolic ligand 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenol (LCl-OH) with MCl2·nH2O in the presence of NH4PF6 or NaClO4 afforded the dinuclear bridged-phenoxido dichlorido-metal(II) complexes [Co2(μ-LClO)(H2O)2Cl2][Co2(μ-LClO)(MeOH)2Cl2](PF6)2 (1), [Ni2(μ-LClO)(MeOH)2Cl2]PF6 (2), [Ni2(μ-LClO)(MeOH)(H2O)Cl2]ClO4·1.25H2O (3), [Cu2(μ-LClO)Cl2]PF6·0.5MeOH (4) and [Zn2(μ-LClO)Cl2]PF6·MeOH (5). The complexes were characterized by elemental microanalyses, cond. measurements, IR and UV-visible spectroscopy, mass spectrometry and single crystal x-ray crystallog. Each M(II) center within the dinuclear complex cations is octahedrally coordinated in complexes 1-3, and five-coordinated distorted square pyramidal in 4 and 5. Magnetic susceptibility measurements at variable temp. of the complexes 1-4 revealed weak to moderate antiferromagnetic coupling with |J| values = 8.38, 39.0, 30.2 and 0.79 cm-1, resp. The results of DFT calcns. correlate well with the exptl. detd. antiferromagnetic coupling and show that the magnetic exchange coupling occurs mainly through the phenoxido bridge M-O-M. Implications of geometry around the central metal ion, M···M distance, M-O-M bond angle and overlapping of magnetic orbitals on the magnetic exchange coupling are discussed. [on SciFinder(R)]",

keywords = "dinuclear transition metal pyridylmethylaminomethylphenolato complex prepn crystal structure magnetism, DFT calcn dinuclear copper cobalt nickel zinc pyridylmethylaminomethylphenolato complex",

author = "Massoud, {Salah S.} and Mark Spell and Ledet, {Catherine C.} and Thomas Junk and Radovan Herchel and Fischer, {Roland C.} and Zdenek Travnicek and Mautner, {Franz A.}",

year = "2015",

doi = "10.1039/C4DT03508A",

language = "English",

volume = "44",

pages = "2110--2121",

journal = "Dalton Transactions",

issn = "1477-9234",

publisher = "Royal Society of Chemistry",

number = "5",

}

TY - JOUR

T1 - Magnetic and structural properties of dinuclear singly bridged-phenoxido metal(II) complexes.

AU - Massoud, Salah S.

AU - Spell, Mark

AU - Ledet, Catherine C.

AU - Junk, Thomas

AU - Herchel, Radovan

AU - Fischer, Roland C.

AU - Travnicek, Zdenek

AU - Mautner, Franz A.

PY - 2015

Y1 - 2015

N2 - The reaction of a methanolic soln. contg. the bi-compartmental phenolic ligand 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenol (LCl-OH) with MCl2·nH2O in the presence of NH4PF6 or NaClO4 afforded the dinuclear bridged-phenoxido dichlorido-metal(II) complexes [Co2(μ-LClO)(H2O)2Cl2][Co2(μ-LClO)(MeOH)2Cl2](PF6)2 (1), [Ni2(μ-LClO)(MeOH)2Cl2]PF6 (2), [Ni2(μ-LClO)(MeOH)(H2O)Cl2]ClO4·1.25H2O (3), [Cu2(μ-LClO)Cl2]PF6·0.5MeOH (4) and [Zn2(μ-LClO)Cl2]PF6·MeOH (5). The complexes were characterized by elemental microanalyses, cond. measurements, IR and UV-visible spectroscopy, mass spectrometry and single crystal x-ray crystallog. Each M(II) center within the dinuclear complex cations is octahedrally coordinated in complexes 1-3, and five-coordinated distorted square pyramidal in 4 and 5. Magnetic susceptibility measurements at variable temp. of the complexes 1-4 revealed weak to moderate antiferromagnetic coupling with |J| values = 8.38, 39.0, 30.2 and 0.79 cm-1, resp. The results of DFT calcns. correlate well with the exptl. detd. antiferromagnetic coupling and show that the magnetic exchange coupling occurs mainly through the phenoxido bridge M-O-M. Implications of geometry around the central metal ion, M···M distance, M-O-M bond angle and overlapping of magnetic orbitals on the magnetic exchange coupling are discussed. [on SciFinder(R)]

AB - The reaction of a methanolic soln. contg. the bi-compartmental phenolic ligand 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenol (LCl-OH) with MCl2·nH2O in the presence of NH4PF6 or NaClO4 afforded the dinuclear bridged-phenoxido dichlorido-metal(II) complexes [Co2(μ-LClO)(H2O)2Cl2][Co2(μ-LClO)(MeOH)2Cl2](PF6)2 (1), [Ni2(μ-LClO)(MeOH)2Cl2]PF6 (2), [Ni2(μ-LClO)(MeOH)(H2O)Cl2]ClO4·1.25H2O (3), [Cu2(μ-LClO)Cl2]PF6·0.5MeOH (4) and [Zn2(μ-LClO)Cl2]PF6·MeOH (5). The complexes were characterized by elemental microanalyses, cond. measurements, IR and UV-visible spectroscopy, mass spectrometry and single crystal x-ray crystallog. Each M(II) center within the dinuclear complex cations is octahedrally coordinated in complexes 1-3, and five-coordinated distorted square pyramidal in 4 and 5. Magnetic susceptibility measurements at variable temp. of the complexes 1-4 revealed weak to moderate antiferromagnetic coupling with |J| values = 8.38, 39.0, 30.2 and 0.79 cm-1, resp. The results of DFT calcns. correlate well with the exptl. detd. antiferromagnetic coupling and show that the magnetic exchange coupling occurs mainly through the phenoxido bridge M-O-M. Implications of geometry around the central metal ion, M···M distance, M-O-M bond angle and overlapping of magnetic orbitals on the magnetic exchange coupling are discussed. [on SciFinder(R)]

KW - dinuclear transition metal pyridylmethylaminomethylphenolato complex prepn crystal structure magnetism

KW - DFT calcn dinuclear copper cobalt nickel zinc pyridylmethylaminomethylphenolato complex

U2 - 10.1039/C4DT03508A

DO - 10.1039/C4DT03508A

M3 - Article

SN - 1477-9234

VL - 44

SP - 2110

EP - 2121

JO - Dalton Transactions

JF - Dalton Transactions

IS - 5

ER -