Australian Journal of Chemistry
Volume 67 Number 11 2014
RESEARCH FRONT: Molecular Magnetism
CH14519An Introduction to Molecular Magnetism: SANZMAG-1 (Southampton-Australia-New Zealand Workshop on Molecular Magnetism)
This special issue highlights work from attendees at SANZMAG-1, a workshop on molecular magnetism which drew together researchers from Australia and New Zealand.
CH14166Polyoxometalate-Supported Lanthanoid Single-Molecule Magnets
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.
CH14381Two-Dimensional Coordination Polymers with Spin Crossover Functionality
Coordination polymers with embedded octahedral iron(ii) spin crossover sites are an important class of electronic switching material. This review focuses specifically on two-dimensional spin crossover polymers of the spin crossover framework (SCOF) and Hofmann-types.
CH14188Thermal Spin Crossover Behaviour of Two-Dimensional Hofmann-Type Coordination Polymers Incorporating Photoactive Ligands
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
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
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
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
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.
CH14385Heterometallic Tetranuclear {Mn2IIILn2III}n 1D Coordination Polymers: Employing Sulfonate Ligands as Connecting Groups
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.
CH14196Magnetic and Electronic Properties of Three New Hetero-Bimetallic Coordination Frameworks [Ru2(O2CR)4][Au(CN)2] (R = Benzoic Acid, Furan-2-carboxylate, or Thiophen-2-carboxylate)
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
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
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.
CH14404Self-Assembly of an Octanuclear High-Spin FeII Molecular Cage
The structure and magnetic properties of an octanuclear iron(ii)-containing cage material of the type [FeII8L12](BF4)16 is reported.
CH14104Protein Immobilization in Metal–Organic Frameworks by Covalent Binding
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.
CH14080Synthesis of Steroid–Porphyrin Conjugates from Oestradiol, Oestrone, and Lithocholic Acid
Four different construction motifs of porphyrin-steroid conjugates are explored and shown in a composite depiction on a porphyrin divided into quadrants.
CH13712Solvent-free Synthesis of Novel Benzothiazole-substituted 4-Thiazolidinones Using Nano Silica-bonded 5-n-Propyl-octahydro-pyrimido[1,2-a]azepinium Chloride as Catalyst
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
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.
CH14038Design of Ionic Liquid-Derived Polyelectrolyte Gels Toward Reversible Water Absorption/Desorption System Driven by Small Temperature Change
Ionic liquid-derived polyelectrolyte gels with moderate hydrophobicity undergo a lower critical solution temperature-type dehydration behaviour.
CH13567Characterisation of Nanostructured Co3O4 Synthesised by the Thermal Decomposition of an Inorganic Precursor
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.
CH13732Organic Molecular Crystals: From Non-Porous Structure to Potential Porous Structure Controlled by Reaction Temperature
This paper describes two novel organic crystals showing non-porous and microporous structures, the formation of which can be precisely controlled by varying the reaction temperature.
CH13675A Series of Enthalpy/Entropy-Driven Reversible Dissolution/Reorganization Equilibriums in the System of Cu(NO3)2–HL–GdX3–H2O (HL=5-methylpyrazine-2-carboxylic acid; X=Cl, Br, NO3, ClO4)
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 1–5 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
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.
CH14074Can Lignin Wastes Originating From Cellulosic Ethanol Biorefineries Act as Radical Scavenging Agents?
Lignins from second-generation biorefinery.
CH14039Colorimetric Assay for Al3+ Based on Alizarin Red S-functionalized Silver Nanoparticles
A simply selective colorimetric assay for Al3+ based on the aggregation of silver nanoparticles functionalized with Alizarin Red S has been developed.
CH14301Water Structure Change-Induced Expansion and Collapse of Zwitterionic Polymers Surface-Grafted onto Carbon Black
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.