Relation between the singlet-triplet splitting and the copper-oxygen-copper bridge angle in hydroxo-bridged copper dimers

Crawford, Van H.; Richardson, H. Wayne; Wasson, John R.; Hodgson, Derek J.; Hatfield, William E.

doi:10.1021/ic50163a019

Cited by 958 publications

(562 citation statements)

References 57 publications

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“…It has been shown that exchange interaction is affected by several structural parameters such as the identity of the bridging atoms (X), the Cu-Cu' distances, the bridging angles Cu-X-Cu' (α), the dihedral angles containing Cu ions and the coordination geometries around copper ions. 5,9,[45][46][47][48][49] For planar dihydroxo-bridged copper complexes, a simple, linear, correlation between the singlet-triplet separation 2J and the angle α was reported. [45][46][47] However, in the case of dihalo-bridged copper complexes, the wider variety of geometries available to such systems and the possibility for relatively low-lying halogens' d-orbitals to interact with copper orbitals make the overall picture more complicated.…”

Section: Magneto-structural Correlationmentioning

confidence: 99%

Crystal structures and magnetic properties of a set of dihalo-bridged oxalamidato copper(ii) dimers

et al. 2014

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A set of four copper(II) complexes, L 1 -X and L 2 -X (X = Cl, Br; L 1 = N-(L-leucine methyl ester)-N'-((2-pyridin-2-yl)methyl)oxalamide and L 2 = N-benzyl-N'-((2-pyridin-2-yl)methyl)oxalamide) have been synthesized and characterized by X-ray structural analysis, electron paramagnetic resonance (EPR) spectroscopy on single crystal and by SQUID magnetization measurements. X-ray diffraction studies show one-dimensional hydrogen bonded networks of dimeric copper(II)-complexes bridged by two halide ions and with the two metal centers 3.44-3.69Å apart. The geometry at each copper(II) atom is ideal or near ideal square pyramidal. EPR and SQUID studies indicate that all complexes exhibit weak antiferromagnetic interactions between the Cu(II) paramagnetic centers, with exchange parameter |J| ∼1 cm −1 . Magneto-structural comparisons among similar dihalo-bridged Cu(II) dinuclear complexes are also provided, and a possible correlation has been established.

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Section: Magneto-structural Correlationmentioning

confidence: 99%

Crystal structures and magnetic properties of a set of dihalo-bridged oxalamidato copper(ii) dimers

et al. 2014

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“…Invented by Hatfield (CRAWFORD et al, 1976;HATFIELD et al, 1985), the exchange coupling constant occurring in the Heisenberg form of the spin Hamiltonian ˆ( ) along a decreasing exponential function: …”

Section: Introductionmentioning

confidence: 99%

MAGNETOSTRUCTURAL J-CORRELATIONS IN Fe(III) COMPLEXES – A REVISION

Vranovičová¹,

Boča²

2013

Nova Biotechnologica Et Chimica

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Abstract:The magnetostructural correlations in Fe(III) complexes, originally outlined by Gorun and Lippard has been revised. Other correlation variants have been tested and the dataset enlarged for more recent entries possessing the Fe-O-Fe bridge including dinuclear, tetranuclear and hexanuclear Fe(III) complexes. The resulting relationships confirm that instead of the original suggestions, the correlation could stay as a linear relationship which covers the possibilities of positive values of exchange coupling constants.

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“…From an experimental point of view, the well-known magnetostructural correlation proposed by Hodgson and Hatfield for the hydroxobridged copper ͑II͒ complexes shows a strong dependence of the magnetic character with the Cu-O-Cu angle. 30 Thus, if this angle has a value larger than 98°, the exchange coupling is found to be antiferromagnetic while for smaller values a ferromagnetic behavior shows up. Our theoretical results have shown that actually there is a second structural parameter that also plays a fundamental role: the out-of-plane shift of the atom bonded to the bridging oxygen.…”

Section: Resultsmentioning

confidence: 95%

Theoretical approach to the magnetostructural correlations in the spin-Peierls compoundCuGeO3

et al. 2000

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A theoretical density-functional study has been carried out to analyze the exchange coupling in the chains of CuGeO 3 using discrete models. The results show a good agreement with the experimental exchange coupling constant ͑J͒ together with a strong dependence of J with the Cu-O-Cu angle. The calculation of the J values for a distorted model indicates a larger degree of dimerization than those reported previously.

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Relation between the singlet-triplet splitting and the copper-oxygen-copper bridge angle in hydroxo-bridged copper dimers

Cited by 958 publications

References 57 publications

Crystal structures and magnetic properties of a set of dihalo-bridged oxalamidato copper(ii) dimers

Crystal structures and magnetic properties of a set of dihalo-bridged oxalamidato copper(ii) dimers

MAGNETOSTRUCTURAL J-CORRELATIONS IN Fe(III) COMPLEXES – A REVISION

Theoretical approach to the magnetostructural correlations in the spin-Peierls compoundCuGeO3

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