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Ni(II)octadecylphosphonate: An Inorganic/Organic Layered Weak Ferromagnet.

Research Abstract
Ni[CH3(CH2)17PO3]·H2O was prepared and characterized by several techniques and the magnetic properties were measured by using a SQUID magnetometer. Preliminary refinement of the X-ray diffraction powder data by structure-less Le Bail fitting could be obtained and the compound was found to crystallise in the orthorhombic space group Pmn21 with a=5.478(7) Å, b=42.31(4) Å, c=4.725(3) Å. Ni(II)octadecyl phosphonate is lamellar and the structure consists of alternating inorganic and organic layers. The inorganic layers are interspersed by by-layers of the octadecyl substituent and van der Waals contacts are established between them. IR spectroscopy revealed all-trans configuration of the hydrocarbonic chain. A tilt angle of 48.2° between the chain axis and the (ac) plane could be estimated. The temperature dependence of the molar susceptibility plotted as 1/χ vs. T is linear above 100 K and it follows the Curie–Weiss law. The Curie, C, constant suggests the presence of Ni(II) ion in the S=1 spin state and the negative Weiss, θ, constant is indicative of antiferromagnetic nearest neighbour exchange interactions. Zero-field and field-cooled χ vs. T plots were then recorded. The plots show no overlap below 20 K, thus indicating that the compound is in an ordered magnetic state. The critical temperature has been located at the onset of the χ vs. T plot and was found to be TN=21 K. The magnetization vs. field plots, measured at different temperatures, provide the indication that the compound is a weak-ferromagnet below TN.
Research Authors
E.M. Bauer, C. Bellitto, S.A. Ibrahim, M.R. Mahmoud and
G. Righini
Research Department
Research Journal
Polyhedron
Research Member
Research Pages
pp , 2463-2469
Research Rank
1
Research Vol
Vol 22 No. 14-17
Research Year
2003

Ni(II)octadecylphosphonate: An Inorganic/Organic Layered Weak Ferromagnet.

Research Abstract
Ni[CH3(CH2)17PO3]·H2O was prepared and characterized by several techniques and the magnetic properties were measured by using a SQUID magnetometer. Preliminary refinement of the X-ray diffraction powder data by structure-less Le Bail fitting could be obtained and the compound was found to crystallise in the orthorhombic space group Pmn21 with a=5.478(7) Å, b=42.31(4) Å, c=4.725(3) Å. Ni(II)octadecyl phosphonate is lamellar and the structure consists of alternating inorganic and organic layers. The inorganic layers are interspersed by by-layers of the octadecyl substituent and van der Waals contacts are established between them. IR spectroscopy revealed all-trans configuration of the hydrocarbonic chain. A tilt angle of 48.2° between the chain axis and the (ac) plane could be estimated. The temperature dependence of the molar susceptibility plotted as 1/χ vs. T is linear above 100 K and it follows the Curie–Weiss law. The Curie, C, constant suggests the presence of Ni(II) ion in the S=1 spin state and the negative Weiss, θ, constant is indicative of antiferromagnetic nearest neighbour exchange interactions. Zero-field and field-cooled χ vs. T plots were then recorded. The plots show no overlap below 20 K, thus indicating that the compound is in an ordered magnetic state. The critical temperature has been located at the onset of the χ vs. T plot and was found to be TN=21 K. The magnetization vs. field plots, measured at different temperatures, provide the indication that the compound is a weak-ferromagnet below TN.
Research Authors
E.M. Bauer, C. Bellitto, S.A. Ibrahim, M.R. Mahmoud and
G. Righini
Research Department
Research Journal
Polyhedron
Research Member
Research Pages
pp , 2463-2469
Research Rank
1
Research Vol
Vol 22 No. 14-17
Research Year
2003

Ni(II), Co(II) and Cu(II) Ternary Complexes Containing
2,4,6-Tris(2-Pyridyl)-1,3,5-triazine as Primary Ligand and Dithiooxamide,Thiosemicarbazide as Secondary Ligands.

Research Abstract
A series of novel dinuclear, mixed-ligand complexes having the general formula [M2(tpt)(L)4]Cl4 · nH2O where M=Ni(II), Co(II) or Cu(II); tpt = 2,4,6-tris(2-pyridyl)-1,3,5-triazine; L = dithiooxamide (dto) or thiosemicarbazide (tsc); n = 2-4, have been synthesized and characterized. The tpt molecule is flexidentate, where it can behave as di- or tridentate dinucleating ligand. The coordination mode of tpt to M(II) apparently occurs through the pyridyl and a triazine nitrogen atoms. All the mixed-ligand complexes are dinuclear with a bridging tpt molecule and having an octahedral structure. The complexes were characterized by chemical analyses, spectral, molar conductance and thermal studies.
Research Authors
S.A. Ibrahim, M.A. El-Gahami, A.M. Hammam and D.M. Fouad
Research Department
Research Journal
Synth.React.Inorg.Met-Org.Chem
Research Member
Research Pages
pp , 1505 - 1514
Research Rank
1
Research Vol
vol. 33 No, 8
Research Year
2003

(II), Ni(II), Cu(II) and Cd(II) Complexes of Some New Arylazo-pyrazolopyrimidine Derivatives.

Research Abstract
The metal ion complexes [Co(II), Ni(II), Cu(II) and Cd(II)] of some azopyrazolopyrimidine derivatives have been prepared and characterized using elemental analyses, molar conductivity, electronic and IR spectra. The azopyrazolopyrimidines are characterized by a high tendency towards complex formation with the neutral molecules coordinating to the metal ion as bidentate ligands. It is concluded that the ligands are bonded to the metal ion through the - or β-nitrogen atom of the arylazo group and the carbonyl oxygen of the pyrazolone ring where six- or five-membered chelate rings are formed. The apparent formation constants of the complexes in solution have been determined.
Research Authors
H.M.A. Salman, A.A. Mohamed, S.A. Ibrahim and A.A. Ahmed
Research Department
Research Journal
Synth.React.Inorg.Met-Org.Chem
Research Member
Research Pages
pp. 1351 - 1366
Research Rank
1
Research Vol
Vol 33 No. 8
Research Year
2003

Adamantane-like Cluster Complexes of Mixed-Valent Copper-Copper and Nickel-Copper Thiolates.

Research Abstract
Square-planar copper(II) and nickel(II) derivatives of the cis-dithiolate N2S2 ligand bis(N,N‘-2-mercapto-2-methylpropyl)-1,5-diazocyclooctane, (bme*daco)M, nucleate four CuICl moieties, forming MII2CuI4S4 clusters with unusual triply bridging thiolates, μ3-SR, in the topological form of adamantane. As determined by X-ray crystallography, the (bme*daco)M (M = Cu or Ni) metallothiolate serves as a bidentate ligand that bridges four CuI ions, utilizing all lone pairs on sulfurs. Further characterization by electrochemical and electronic spectral measurements suggests greater electron delocalization in the all-copper complex as compared to the NiCu heterometallic complex. Mass spectral data imply that the mixed-metal NiII2CuI4S4 is more stable toward CuCl loss than CuII2CuI4S4, a result that is corroborated by extraction of CuI by 1,2-bis(diphenylphosphino)ethane in the latter but not the former.
Research Authors
M.L. Miller, S.A. Ibrahim, M.L. Golden, M.Y. Darensbourg
Research Department
Research Journal
Inorg.Chem
Research Member
Research Pages
pp 2999–3007
Research Rank
1
Research Vol
Vol 42 No. 9
Research Year
2003

Synthesis, X-Ray Powder Structure and Magnetic Properties of Layered Ni(II) Methyl- and Octadecylphosphonates.

Research Abstract
[Ni(CH3PO3)(H2O)] (1) and [Ni{CH3-(CH2)17-PO3}(H2O)] (2) were synthesised by reaction of NiCl26 H2O and the relevant phosphonic acid in water in presence of urea. The compounds were characterised by elemental and thermogravimetric analyses, UV-visible and IR spectroscopy, and their magnetic properties were studied by using a SQUID magnetometer. The crystal structure of 1 was determined ab initio from X-ray powder diffraction data and refined by the Rietveld method. The crystals of 1 are orthorhombic, space group Pmn21, with a=5.587(1), b=8.698(1), c=4.731(1) Å. The compound has a hybrid, layered structure made up of alternating inorganic and organic layers along the b direction of the unit-cell. The inorganic layers consist of NiII ions octahedrally coordinated by five phosphonate oxygen atoms and one oxygen atom from the water molecule. These layers are separated by bilayers of methyl groups and van der Waals contacts are established between them. A preliminary structure characterisation of compound 2 suggests the crystallisation in the orthorhombic system with the following unit-cell parameters: a=5.478(7), b=42.31(4), c=4.725(3) Å. The oxidation state of the Ni ion in both compounds is +2, and the electronic configuration is d8 (S=1), as determined from static magnetic susceptibility measurements above 50 K. Compound 1 obeys the Curie-Weiss law at temperatures above 50 K; the Curie (C) and Weiss () constants were found to be 1.15 cm3 K mol-1 and -32 K, respectively. The negative value of indicates an antiferromagnetic exchange coupling between near-neighbouring NiII ions. No sign of 3D antiferromagnetic long-range order is observed down to T=5 K, the lowest measured temperature. Compound 2 is paramagnetic above T=50 K, and the values of C and were found to be 1.25 cm3 K mol-1 and -24 K, respectively. Below 50 K the magnetic behavior of 2 is different from that of 1. Zero-field cooled (zfc) and field-cooled (fc) magnetisation plots do not overlap below T=21 K. The irreversible magnetisation, Mfc-zfc, obtained as a difference from fc and zfc plots starts to increase at T=20 K, on lowering the temperature, and it becomes steady at T=5 K. The presence of spontaneous magnetisation below T=20 K indicates a transition to a weak-ferromagnetic state for compound 2.
Research Authors
C. Bellitto, E.M. Bauer, S.A. Ibrahim, M.R. Mahmoud and G. Righini
Research Department
Research Journal
Chem. Eur.J.
Research Member
Research Pages
pp .1324 - 1331
Research Rank
1
Research Vol
Vol 9 No. 6
Research Year
2003

Synthesis, X-Ray Powder Structure and Magnetic Properties of Layered Ni(II) Methyl- and Octadecylphosphonates.

Research Abstract
[Ni(CH3PO3)(H2O)] (1) and [Ni{CH3-(CH2)17-PO3}(H2O)] (2) were synthesised by reaction of NiCl26 H2O and the relevant phosphonic acid in water in presence of urea. The compounds were characterised by elemental and thermogravimetric analyses, UV-visible and IR spectroscopy, and their magnetic properties were studied by using a SQUID magnetometer. The crystal structure of 1 was determined ab initio from X-ray powder diffraction data and refined by the Rietveld method. The crystals of 1 are orthorhombic, space group Pmn21, with a=5.587(1), b=8.698(1), c=4.731(1) Å. The compound has a hybrid, layered structure made up of alternating inorganic and organic layers along the b direction of the unit-cell. The inorganic layers consist of NiII ions octahedrally coordinated by five phosphonate oxygen atoms and one oxygen atom from the water molecule. These layers are separated by bilayers of methyl groups and van der Waals contacts are established between them. A preliminary structure characterisation of compound 2 suggests the crystallisation in the orthorhombic system with the following unit-cell parameters: a=5.478(7), b=42.31(4), c=4.725(3) Å. The oxidation state of the Ni ion in both compounds is +2, and the electronic configuration is d8 (S=1), as determined from static magnetic susceptibility measurements above 50 K. Compound 1 obeys the Curie-Weiss law at temperatures above 50 K; the Curie (C) and Weiss () constants were found to be 1.15 cm3 K mol-1 and -32 K, respectively. The negative value of indicates an antiferromagnetic exchange coupling between near-neighbouring NiII ions. No sign of 3D antiferromagnetic long-range order is observed down to T=5 K, the lowest measured temperature. Compound 2 is paramagnetic above T=50 K, and the values of C and were found to be 1.25 cm3 K mol-1 and -24 K, respectively. Below 50 K the magnetic behavior of 2 is different from that of 1. Zero-field cooled (zfc) and field-cooled (fc) magnetisation plots do not overlap below T=21 K. The irreversible magnetisation, Mfc-zfc, obtained as a difference from fc and zfc plots starts to increase at T=20 K, on lowering the temperature, and it becomes steady at T=5 K. The presence of spontaneous magnetisation below T=20 K indicates a transition to a weak-ferromagnetic state for compound 2.
Research Authors
C. Bellitto, E.M. Bauer, S.A. Ibrahim, M.R. Mahmoud and G. Righini
Research Department
Research Journal
Chem. Eur.J.
Research Member
Research Pages
pp .1324 - 1331
Research Rank
1
Research Vol
Vol 9 No. 6
Research Year
2003
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