Rebecca H. Laye

A family of heterometallic wheels containing potentially fourteen hundred siblings

The synthesis and structure of new heterometallic wheels are reported, with preliminary studies of selected compounds.

Ferromagnetic Ni(II) discs.

A family of planar disc-like hexa-, octa- and decametallic Ni(II) complexes exhibit dominant ferromagnetic exchange. The deca- and octametallic clusters [Ni(II) (10)(tmp)(2)(N(3))(8)(acac)(6)(MeOH)(6)] (1, H(3)tmp=1,1,1-tris(hydroxymethyl)propane; acac=acetylacetonate) and [Ni(II) (8)(thme)(2)(O(2)CPh)(4)(Cl)(6)(MeCN)(6)(H(2)O)(2)] (2, H(3)thme=1,1,1-tris(hydroxymethyl)ethane) represent rare examples of Ni(II)-based single-molecule magnets, and [Ni(II) (10)] (1) possesses the largest barrier to magnetisation reversal of any Ni(II) single-molecule magnet to date.

The coordination chemistry of fluorescent pyridinyl– and quinolinyl–phthalimide ligands with the {AuI–PPh3} cationic unit

The new mono-dentate ligands, 2-(2-aminoethyl)-N-phthalimido-pyridine () and 8-amino-N-phthalimido-quinoline (), were synthesised using a solvent-free melt method. These ligands together with (3-amino-N-phthalimido-pyridine; 3-aminomethyl-N-phthalimido-pyridine; 4-aminomethyl-N-phthalimido-pyridine; 3-amino-N-phthalimido-quinoline) were then used to access six luminescent Au(I) complexes of the generic type {Ph(3)P-Au-L(n)}(OTf). X-Ray crystallography has been used to structurally characterise three of the complexes showing that in the cases of and the complexes adopt an approximately linear P-Au-N coordination geometry. However, in the case of the sterically demanding the structure shows distortions within the ligand and deviations from a linear coordination geometry. Solution state (1)H and (31)P{(1)H} NMR confirmed that the proposed formulations and coordination modes exist in solution. At room temperature the photophysical studies showed that the emission from each of the six complexes was in the visible region (395-475 nm) and assigned to a ligand-centred fluorescence (tau < 10 ns) in each case.

A high-nuclearity, beyond “fully reduced” polyoxo(alkoxo)vanadium(III/IV) cage

The solvothermal synthesis, crystal structure and preliminary magnetic studies are reported of the first high nuclearity V(III)-based polyoxo(alkoxo)vanadium cage, a V(III)16V(IV)2 complex.

Hexanuclear Fe(III) complexes and their thermal decomposition into an undecanuclear species

The anion of the amino-alcohol 3-dimethylamino-2-propanol has been used to prepare a family of hexanuclear Fe(III) complexes of general formula [Fe6O2(OH)2(RCO2)10(C5H12NO)2] (R = Me: 1, R = Ph: 2, R = m-MeC6H4: 3, R = o-MeC6H4: 4). The complexes have been characterized by single-crystal X-ray diffraction, IR and elemental analyses. The study of their magnetic properties reveals spin-ground states from S = 2 to S = 5. The thermal decomposition of the [Fe6] complexes results in the loss of the aminoalcohol ligands and the solid state formation of undecanuclear complexes.

Stereostructural behaviour of N-N atropisomers: Two conglomerate crystallisations and a crystallisation-induced deracemisation

The solid state behaviour of a number of compounds which show hindered rotation around an N–N bond, in some cases leading to axial chirality is described. A diacyl hydrazine, bisanthranoly hydrazine, 1 crystallises in the chiral space group P212121, presenting an example of conglomerate crystallisation. A tetra-acyl hydrazine derived from lactic acid, 2, shows kinetic resolution by crystallisation, as of the two isomers observed in the solution NMR, only one crystallises, again in the space group P212121. Two cyclic acyl hydrazines in the form of biquinazolinones are studied: 2,2′diphenyl-3,3-biquinazolinone, 3 crystallises in the achiral space group Pbca, while 3,3′-dimethyl-2,2′-biquinazoline-4′-thio-4-one, 4 crystallises in the chiral space group P21 giving another example of a conglomerate crystallisation. The single crystal structures of each of the species have been compared to powder XRD data to confirm that the single crystal structures are representative of the bulk material.

Supertetrahedral decametallic Ni(ii) clusters directed by 6-tris-alkoxidesElectronic supplementary information (ESI) available: disordered ethanol and benzoate on the Ni6, Ni7, Ni6A edge. See http://www.rsc.org/suppdata/cc/b4/b403876b/

We report the syntheses, structures and magnetic properties of two decametallic Ni(II) clusters with unprecedented supertetrahedral cores, stabilised by the (hitherto unobserved) μ6-coordination modes of the tris-alkoxides {MeC(CH2O)3}3− and {C6H9O3}3−.