Magnetic properties of the complex di-.mu.-hydroxo-bis[2-(2-ethylaminoethyl)pyridine]dicopper(II) perchlorate

Jeter, David Y.; Lewis, David L.; Hempel, Judith C.; Hodgson, Derek J.; Hatfield, William E.

doi:10.1021/ic50114a050

Cited by 48 publications

(12 citation statements)

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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%

“…5,9,[46][47][48][49][50] For planar dihydroxo-bridged copper complexes, a simple, linear, correlation between the singlet-triplet separation 2J and the angle α was reported. [46][47][48] 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. 51 Generally, a strong correlation ( parabolic curve with a maximum of ca.…”

Section: Magneto-structural Correlationmentioning

confidence: 99%

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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%

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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“…-205 (12) 1323 ( 23) 414 ( 7) Br( 2) 3705 (4) 394( 4) 2803 (27) -447 (11) 1403 (3) 13( 8) 0(1) 209 (15) 21 (2) 81( 7) 6 (5) 58( 9) 12 (3) C(l) 176 ( 26) 44 ( 4) 125 ( 14)…”

Section: Dicussionunclassified

Structural and magnetic characterization of the alkoxo-bridged chromium(III) dimers di-.mu.-methoxy-bis[bis(3-bromo-2,4-pentanedionato)chromium(III)] and di-.mu.-ethoxy-bis[bis(3-bromo-2,4-pentanedionato)chromium(III)]

Estes¹,

Scaringe²,

Hatfield³

et al. 1977

Inorg. Chem.

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The crystal structures of the complexes di-~-methoxy-bis[bis(3-bromo-2,4-pentanedionato)chromium(III)], a~a c )~O C H~l 2, and di-~-ethoxy-bis[bis(3-bromo-2,4-pentanedionato)chromium(III)] , [ C r ( 3 -B r -a c a~)~O C~H~]~, have been determined from three-dimensional counter x-ray data. The methoxy complex crystallizes in the monoclinic space group P2Jc with two dimeric formula units in a cell of dimensions a = 7.769 (7) A, b 18.587 (21) A, c = 11.353 (10) A, and @ = 112.99 (4)". Least-squares refinement of 1366 independent data has led to a final R factor (on F) of 0.034; this complex is isomorphous with the 3-chloro analogue. The ethoxy complex also crystallizes in the monoclinic space group P2,/c in a cell of dimensions a = 8.428 (3) A, b = 19.339 (7) A, c = 11.376 (4) A, and p = 109.10 (1)'. Least-squares refinement of 1151 data has led to an R factor (on F) of 0.046. Both complexes consist of two chromium(II1) ions which are symmetrically bridged by two alkoxide groups, the remaining coordination sites being occupied by the oxygen atoms of two bidentate 3-Br-acac ligands. The coordination around each chromium center is roughly octahedral; in the methoxy complex the average Cr-O(1igand) bond length is 1.958 (5) A, the Cr-Cr separation is 3.038 (3) A, and the Cr-0-Cr bridging angle is 101.5 (2)' while the corresponding values in the ethoxy complex are 1.952 (8) A, 3.027 (3) A, and 101.8 (3)'. The 3-Br-acacligands are approximately planar. The magnetic susceptibilities of powdered samples of the complexes have been examined in the temperature range 4-100 K. The dimers exhibit antiferromagnetic exchange interactions with the best fit to the Van Vleck equation including biquadratic exchange yielding 2 J = -7.10 cm-' a n d j = 0.22 cm-' with ( g ) = 1.932 for the methoxy complex and 2 J = -17.88 cm-',j = 0, and ( g ) = 1.945. The data for the methoxy complex are similar to those for the corresponding 3-chloro complex and lead to a singlet-triplet splitting of -8.53 cm-', but those for the ethoxy complex show stronger magnetic coupling which can be attributed to the greater electron density at the bridging oxygen atom in this case.

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“…Hatfield Jeter, Lewis, Hempel, Hodgson & Hatfield, 1972) and similar studies on the analogous systems [Cu(bipy)OH] 2+, where bipy is 2,2'-bipyridine (Casey, Hoskins & Whillans, 1970;Majeste & Meyers, 1970;Barnes, Hodgson & Hatfield, 1972) and [Cu(tmen)OH] 2+, where tmen = tetramethylethylenediamine (Mitchell, Bernard & Wasson, 1970;Cole & Brumage, 1970) we were able to deduce that the value of 2J, the singlet-triplet energy separation, decreases as the Cu-O-Cu bridging angle ~0 increases, and that 2J changes from positive to negative in the region 97 to 99 ° .…”

Section: Introductionmentioning

confidence: 99%

The crystal and molecular structure of di-μ-hydroxobis[di(1,10-phenanthroline)chromium(III)] chloride hexahydrate

Veal¹,

Hatfield²,

Hodgson³

1973

Acta Crystallogr Sect B

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THE STRUCTURES OF FLUORIDES. Iresult of decreasing stability of the octahedral structure with decreasing cation size, with a consequent tendency to form fivefold and, finally, tetrahedral coordination. In the alkali metal niobates (Megaw, 1968b) The Crystal and Molecular Structure of Di-~t-hydroxobisldi(1,10-phenanthroline)chromium(III)l Chloride Hexahydrate BY JACK T. VEAL,* WILLIAM E. HATFIELD AND DEREK J. HODGSONt Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27514, U.S.A. (Received 17 May 1972; accepted 14 September 1972)The crystal and molecular structure of di-/t-hydroxobis[di(1,10-phenanthroline)chromium(IlI)] chloride hexahydrate, [Cr(phen)2OH]2Cla.6H20, has been determined from three-dimensional counter X-ray data. The material crystallizes in the triclinic space group PI with two dimeric formula units in a cell whose dimensions are a= 14.056 (7), b= 11.296 (6), c= 18.990 (9) A, ~=87.15 (3), fl= 107-63 (2), and ),=74.68 (3) °. The observed and calculated densities are 1.39 (4) and 1.342 g cm -3 respectively. The structure has been refined by full-matrix least-squares techniques to a conventional R value of 0.077 for 3392 independent intensities greater than three times their estimated standard deviations. The complex consists of pairs of chromium atoms which are linked by two hydroxo bridges, with two 1,10-phenanthroline groups coordinated to each metal; the coordination geometry around each chromium is roughly octahedral. The average Cr-N and Cr-O bond lengths are 2-052 (6) and 1.927 (6) .~, respectively, while the Cr-Cr separation is 3.008 (3) ,& and the average Cr-O-Cr angle is 102-7 (4) °. The geometry of this complex is compared with that of [Cr(gly)2OH]2 and with those of complexes of the type [CuLOH]~. +, and the magnetic properties of the complex are discussed in terms of the bridging geometry.

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Magnetic properties of the complex di-.mu.-hydroxo-bis[2-(2-ethylaminoethyl)pyridine]dicopper(II) perchlorate

Cited by 48 publications

References 1 publication

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

Structural and magnetic characterization of the alkoxo-bridged chromium(III) dimers di-.mu.-methoxy-bis[bis(3-bromo-2,4-pentanedionato)chromium(III)] and di-.mu.-ethoxy-bis[bis(3-bromo-2,4-pentanedionato)chromium(III)]

The crystal and molecular structure of di-μ-hydroxobis[di(1,10-phenanthroline)chromium(III)] chloride hexahydrate

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