Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
Australian Journal of Chemistry

Australian Journal of Chemistry

Volume 67 Number 11 2014

RESEARCH FRONT: Molecular Magnetism

CH14166Polyoxometalate-Supported Lanthanoid Single-Molecule Magnets

Michele Vonci and Colette Boskovic
pp. 1542-1552
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Lanthanoid-based single-molecule magnets (Ln-SMMs) hold clear promise for the achievement of large energy barriers to magnetisation reversal. The structural and electronic versatility of polyoxometalates renders them a useful class of supporting ligands for Ln-SMMs. This review discusses Ln-SMMs with polyoxometalate ligands, focusing on structure, magnetic properties, and magnetostructural correlations.

CH14188Thermal Spin Crossover Behaviour of Two-Dimensional Hofmann-Type Coordination Polymers Incorporating Photoactive Ligands

Florence Ragon, Korcan Yaksi, Natasha F. Sciortino, Guillaume Chastanet, Jean-François Létard, Deanna M. D'Alessandro, Cameron J. Kepert and Suzanne M. Neville
pp. 1563-1573
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A family of 2D Hofmann-type polymeric materials containing the photoactive ligands 3- and 4-phenylazo-pyridine are presented. They each show thermal and light-induced spin crossover behaviours.

CH14177Steric Trapping of the High Spin State in FeIII Quinolylsalicylaldimine Complexes

Darunee Sertphon, David J. Harding, Phimphaka Harding, Keith S. Murray, Boujemaa Moubaraki and Harry Adams
pp. 1574-1580
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A novel ligand, N-(8-quinolyl)-5-tert-butylsalicylaldimine (Hqsal-5-tBu) is prepared and a series of FeIII complexes, [FeIII(qsal-5-tBu)2]+ studied. Strong structural distortions caused by the ligand result in the complexes becoming trapped in the high spin state.

CH14207Magnetic Exchange Effects in {CrIII2DyIII2} Single Molecule Magnets Containing Alcoholamine Ligands

Stuart K. Langley, Daniel P. Wielechowski, Boujemaa Moubaraki, Brendan F. Abrahams and Keith S. Murray
pp. 1581-1587
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The detailed structural and magnetic properties of a family of {CrIII2DyIII2}–alcoholamine cluster complexes reveal single molecule magnetism properties with strongly coercive hysteresis loops at temperatures up to 3.5 K, the strong intra-cluster magnetic exchange being responsible for these features.

CH14136Magnetic Studies of Metal Ion Coordination Clusters Encapsulated with Thiacalixarene

Rebecca O. Fuller, Karen L. Livesey, Robert C. Woodward, Allan J. McKinley, Brian W. Skelton and George A. Koutsantonis
pp. 1588-1594
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Three thiacalixarene (LH4) metal complexes, [Fe3O(L)2]·1.3CH2Cl2·2H2O·5C3H7NO (1), [Cu4(L)2]·1.5CH2Cl2·C3H7NO (2), and [(μ-H2O)Eu2(LH)2(C3H7NO)4]·2CH3CN·1.5C3H7NO (3) have been prepared for detailed magnetic studies. These complexes were found to exhibit interesting exchange coupling that is the direct result of the molecular features.

CH14145Solvent Dependent Spin-State Behaviour via Hydrogen Bonding in Neutral FeII Diimine Complexes

Kelsey A. Schulte, Stephanie R. Fiedler and Matthew P. Shores
pp. 1595-1600
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To use spin-crossover as a reporter for chemical sensing, it is important to understand how the local environment influences the complex’s spin state. The FeII pyridyl–imidazoline complexes described here allow us to separately assess the effects of external hydrogen bond donors, acceptors, and the intrinsic ligand fields.

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The structures and magnetism of a new family of 1D heterometallic complexes {Mn2IIILn2III}n (Ln = Pr, Nd, Gd, Tb, Dy) are described with the exchange parameters deduced for the Gd complex. Slow magnetisation reversal was noted for the Dy complex in the alternating current susceptibility data when measured in an applied direct current field.

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Three new coordination frameworks, [Ru2(O2CR)4][Au(CN)2] (R = phenyl (1(Ph)), 2-furan (1(Furan)), and 2-thiophene (1(Thio)), are reported. Modulation of the one-dimensional chain structure, with resulting influence on the magnetic and electronic properties of these frameworks, has been achieved through systematic variation of the carboxylate ligands.

CH14389Structural Disorder and Classical Spin-Glass Behaviour in Ba3Fe2SbO9

Josie E. Auckett, Wojciech Miiller, Maxim Avdeev, Justin A Kimpton and Chris D. Ling
pp. 1612-1617
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A new 6H-type perovskite Ba3Fe2SbO9 has been synthesised. It has a partially disordered 6H-type perovskite structure which has been studied by synchrotron and neutron powder diffraction, and displays classical spin-glass behaviour as characterised by magnetic susceptibility, magnetisation, and heat capacity measurements.

CH14390Manganese(II) Oxazolidine Nitroxide Chelates: Structure, Magnetism, and Redox Properties

Ian A. Gass, Mousa Asadi, David W. Lupton, Boujemaa Moubaraki, Alan M. Bond, Si-Xuan Guo and Keith S. Murray
pp. 1618-1624
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The nitroxide radical complex [MnII(L)2](ClO4)2, where L = 4-dimethyl-2,2-di(2-pyridyl)oxazolidine N-oxide, displays antiferromagnetic exchange between the MnII S = 5/2 centre and the two ligand S = 1/2 centres, yielding an S = 3/2 spin ground state. The electrochemical properties are interpreted in terms of square reaction schemes involving metal and ligand redox processes.

CH14104Protein Immobilization in Metal–Organic Frameworks by Covalent Binding

Xuan Wang, Trevor A. Makal and Hong-Cai Zhou
pp. 1629-1631
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Studies on biocatalysis in industry exploded during the last decade to solve the energy issue; however, the poor stability of enzymes hampers the development of this field. Recent investigations on enzyme immobilization on metal–organic frameworks show great potential to achieve a highly efficient catalytic system, where the covalent binding is of great significance.

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Benzothiazole and thiazolidinone derivatives are interesting compounds in the area of medicinal chemistry. In this paper, a series of novel benzothiazole-substituted 4-thiazolidinones were synthesised by the one-pot reaction of rhodanine-3-acetic acid derivatives, 2-aminothiophenol, and triphenylphosphite using nano silica-bonded 5-n-propyl-octahydro-pyrimido[1,2-a]azepinium chloride as heterogeneous reusable nanocatalyst under solvent-free conditions in high yields.

CH13713Novel Synthesis, Molecular Structure, and Theoretical Studies of Dispiro Compounds via Pseudo-eight-component Reaction

Nourallah Hazeri, Mojtaba Lashkari, Santiago García-Granda and Laura Torre-Fernández
pp. 1656-1665
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We have developed a diastereoselective synthesis of dispiro compounds through a one-pot domino pseudo-eight-component reaction of amines, aldehydes, and Meldrum’s acid. This method resulted in the generation of complex products with four stereocentres and involves formation of 10 new bonds.

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Nanocrystalline Co3O4 has been synthesised from the inorganic precursor Co(cinnamate)2(N2H4)2 via the thermal decomposition route. Using appropriate annealing conditions, the precursor yielded cobalt oxide nanoparticles of average size ~11 nm. The nanoparticles were characterised for their size and structure using X-ray diffraction, high-resolution transmission electron microscopic, selected area electron diffraction and scanning electron microscopic techniques.

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It is important for the directional design and preparation of molecule-based functional materials to explore the self-assembly behaviour of reaction components. In the present research, it is reported that a series of reversible dissolution/reorganization equilibriums between the initial reactant with the final products 15 occur in aqueous systems, which were determined to be enthalpy/entropy driven chemical equilibriums by single crystal X-ray diffraction and microcalorimetry.

CH13722Synthesis of Flame-retardant Phosphaphenanthrene Derivatives with High Phosphorus Contents

Jinyun Zheng, Yujian Yu, Lulu Zhang, Xiaomin Zhen and Yufen Zhao
pp. 1688-1692
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Two novel types of high-density phosphorus DOPO derivatives were designed, synthesised, and characterised. The compounds were used as flame retardant additives in Li-ion batteries for the first time. The high-density phosphorus DOPO compounds have good thermal stability, high char yields, and effective flame retardant properties.

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The expansion and collapse of surface-grafted zwitterionic polymer brushes in water caused by the addition of urea is demonstrated. We hypothesize that this is an effect of change in water structure causing change in solvation of the brushes and hence a change in the dipole–dipole interaction, and that it is analogous to the effects of urea on protein stability.

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Professor Kenneth Seddon OBE, one of AJC’s longest-standing Editors, sadly passed away on 21 January from prostate cancer. Ken was one of the world's best ionic liquids experts. His consistent unwavering support, loyalty and advocacy for AJC over the last 10 years will be sorely missed.