Phimphaka Harding

Abrupt spin crossover in an iron(III) quinolylsalicylaldimine complex: structural insights and solvent effects

The first Fe(III) qsal-X complex exhibiting abrupt complete spin crossover at 228 K with a hysteresis of 8 K, [Fe(qsal-I)2]OTf is reported. Structural studies of the MeOH solvate in the LS and HS state and at the spin transition are described.

FeIII Quinolylsalicylaldimine Complexes: A Rare Mixed‐Spin‐State Complex and Abrupt Spin Crossover

A new synthesis of (8-quinolyl)-5-methoxysalicylaldimine (Hqsal-5-OMe) is reported and its crystal structure is presented. Two Fe(III) complexes, [Fe(qsal-5-OMe)(2)]Cl⋅solvent (solvent = 2 MeOH⋅0.5 H(2)O (1) and MeCN⋅H(2)O (2)) have been prepared and their structural, electronic and magnetic properties studied. [Fe(qsal-5-OMe)(2)]Cl⋅2 MeOH⋅0.5 H(2)O (1) exhibits rare crystallographically independent high-spin and low-spin Fe(III) centres at 150 K, whereas [Fe(qsal-5-OMe)(2)]Cl⋅ MeCN⋅H(2)O (2) is low spin at 100 K. In both structures there are extensive π-π and C-H⋅⋅⋅π interactions. SQUID magnetometry of 2 reveals an unusual abrupt stepped-spin crossover with T(1/2) = 245 K and 275 K for steps 1 and 2, respectively, with a slight hysteresis of 5 K in the first step and a plateau of 15 K between the steps. In contrast, 1 is found to undergo an abrupt half-spin crossover also with a hysteresis of 10 K. The two compounds are the first Fe(III) complexes of a substituted qsal ligand to exhibit abrupt spin crossover. These conclusions are supported by (57) Fe Mössbauer spectroscopy. Both complexes exhibit reversible reduction to Fe(II) at -0.18 V and irreversible oxidation of the coordinated qsal-5-OMe ligand at +1.10 V.

Synthesis and Electrochemical Studies of Nickel β-Diketonate Complexes Incorporating Asymmetric Diimine Ligands

The reaction of ppaX {(4-X-phenyl)-pyridin-2-ylmethylene-amine; X = H, Me, Et, OMe, F, Cl, Br, and I} with [Ni(β-diketonate)2(H2O)2] {β-diketonate = 1,3-diphenylpropanedionate (dbm), 2,2,6,6-tetramethyl-3,5-heptadionate (tmhd), or hexafluoroacetylacetonate (hfac)} yields a series of nickel complexes. X-ray crystallography reveals octahedral coordinated nickel centres with a cis arrangement of the β-diketonate ligands. The β-diketonate ligands adopt ‘planar’ or ‘bent’ coordination modes, whereas the aryl ring of the ppaX ligand is twisted with respect to the pyridylimine unit. The electrochemical behaviour of the complexes reveals quasi-reversible or irreversible one-electron oxidation to Ni(iii) in the case of the [Ni(tmhd)2(ppaX)] and [Ni(dbm)2(ppaX)] complexes, respectively. The peak potential for oxidation is dependent on the type of β-diketonate ligand but essentially independent of the substituent, X, on the ppaX ligand. The [Ni(β-diketonate)2(ppaX)] complexes (X = F, Cl, Br, and I) also undergo ligand based reduction.

Synthesis and Characterization of CoFe2O4 Particle by PVA Sol-Gel Method

Cobalt ferrite (CoFe2O4) is a soft magnetic material that can be used as fillers in polypropylene. This magnetic polymer composite is studied for its electromagnetic wave absorbing property. To synthesize CoFe2O4 by the polyvinyl alcohol (PVA) sol-gel method, PVA powder was dissolve in distilled water with 5%, 10% and 15% weight per volume. The solution was stirred and regulated at temperature between 60-80°C until turning into PVA gel. Fe and Co powder of atomic ratio 2:1 were then added to the PVA gel with the metal weight per gel volume 1:6, 1:10 and 1: 12. After sintering at 800°C, phases of the synthesized powder were identified by X-ray diffraction (XRD). Magnetic properties of CoFe2O4 were characterized in order to select the appropriate synthesis condition for electromagnetic wave absorbers.

Tris(phenanthroline-κN,N')cobalt(II) tetra-fluoridoborate acetonitrile solvate.

In the crystal structure of the title compound, [Co(C12H8N2)3](BF4)2·CH3CN, the molecular packing involves dimers of distorted octahedrally coordinated cations which are held together by one π–π [centroid–centroid = 3.542 (4) Å] and two C—H⋯π interactions [2.573 (4) Å] resulting in a P4AE (Parallel Fourfold Aryl Embrace) motif. The anions are found in aryl boxes formed from the phenanthroline ligands.

Steric Trapping of the High Spin State in FeIII Quinolylsalicylaldimine Complexes

A new sterically bulky Schiff base ligand, N-(8-quinolyl)-5-tert-butylsalicylaldimine (Hqsal-5-tBu) has been prepared and a series of FeIII complexes, [Fe(qsal-5-tBu)2]Y (Y = Cl 1, ClO4 2, NO3 3, BF4 4) utilising this ligand are reported and fully characterised. UV-vis spectroscopic and electrochemical studies indicate that 1–4 are high spin (HS) in solution at room temperature and further suggest that the tBu group only slightly alters the electronic properties of 1–4 compared with related [Fe(qsal-5-X)2]+ systems. The structures of [Fe(qsal-5-tBu)2]Cl·4MeOH·H2O 1, [Fe(qsal-5-tBu)2]ClO4·MeOH 2, and [Fe(qsal-5-tBu)2]NO3 3 determined at 100 K reveal HS FeIII centres in all cases. Four-fold parallel aryl embraces and π–π interactions serve to link the cations forming 2D sheets mirroring the motifs found in other [Fe(qsal-5-X)2]+ complexes. Despite this the tBu group causes strong distortions at the Fe centre which as magnetic studies reveal prevent spin crossover trapping 1–4 in the HS state.

Structural and magnetic properties of cobalt ferrites synthesized using sol-gel techniques

Cobalt ferrite (CoFe2O4) was synthesized using sol-gel techniques from cobalt nitrate: iron nitrate: polyvinyl alcohol (PVA) gel in a ratio of 1:2:12. Variations in the amount of PVA in water (5 %, 10 % and 15 %) influenced the crystallite size and phases of the ferrite products, which in turn controlled their magnetic properties. X-ray diffraction studies indicated single phase CoFe2O4 with larger crystallite size and with the hysteresis loops displaying an increase in both coercive field and squareness as the PVA content was increased. Differential scanning calorimetry (DSC) showed that desorption of water and combustion of excess gel were clearly observed in CoFe2O4 prepared from 10 % and 15 % PVA in water. In the case of 5 % PVA in water, two other ratios of cobalt nitrate: iron nitrate: PVA solution were also tested and it was found that the 1:2:10 ratio led to the smallest coercive field and squareness.

Microwave‐Assisted Synthesis of N,N′‐Disubstituted Acetamidine Ligands

Abstract Under microwave activation, triethylorthoacetate reacts with the substituted anilines in the presence of acetic acid as a catalyst, producing acetamidine in moderate to high yields. The X‐ray structures of the new amidines, N,N′‐bis(3,5‐dimethylphenyl)‐acetamidine and N,N′‐bis(p‐tolyl)acetamidine, are also reported, revealing polymeric chains supported by intramolecular H‐bonds.

Tris(5-methyl-3-phenyl-1H-pyrazol-1-yl)methane.

The first crystal structure of a second-generation tris(pyrazolyl)methane, namely the title compound, C31H28N6, is reported. The molecule exhibits a helical conformation with an average twist of 35.1°. In addition, there are C—H⋯π interactions of 3.202 (2) Å between the pyrazole C—H group and neighbouring phenyl groups.

Copper hydrotris(3,5-diphenylpyrazolyl)borate dithiocarbamates: mimicking green copper proteins

Three novel copper hydrotris(3,5-diphenylpyrazolyl)borate (TpPh2) dithiocarbamate complexes, [TpPh2Cu(dtc)] (dtc = S2CNEt21, S2CNBz22 and S2CN(CH2)43) have been prepared in a simple one pot reaction by sequential addition of KTpPh2 and Na(dtc) to CuCl2·2H2O. IR, UV-Vis and ESR spectroscopic studies suggest a mostly κ3 coordinated TpPh2 ligand, bidentate dithiocarbamate ligands and therefore, a five coordinate copper centre. Unusually, a κ3 to κ2 isomerisation of the TpPh2 ligand is found in solution in 3 and to a lesser extent in 1. The X-ray crystal structures reveal geometries intermediate between trigonal bipyramidal and square pyramidal depending on the steric bulk of the dithiocarbamate ligand and a long Cu–N bond resulting in an asymmetrically bound TpPh2 ligand. Electrochemical studies reveal quasi-reversible one-electron oxidation and reduction to Cu(I) with the reversibility and reduction potential strongly dependent on the dithiocarbamate. DFT calculations reveal a weakly antibonding Cu–S π* SOMO and a strongly antibonding Cu–S σ* LUMO consistent with the significant effect of the dithiocarbamate ligand on the electrochemical behaviour of these complexes.