Fraser J. White

Antiferromagnetic versus Ferromagnetic Exchange Interactions in Bis(μ-Ooximate)dinickel(II) Units for a Series of Closely Related Cube Shaped Carboxamideoximate-Bridged Ni4 Complexes. A Combined Experimental and Theoretical Magneto-Structural Study

The syntheses, crystal structures, and the experimental and theoretical magnetochemical characterization for three tetrametallic Ni(II) clusters, namely, [Ni(4)(L)(4)(Cl)(2)(MeOH)(2)](ClO(4))(2)·4MeOH (1), [Ni(4)(L)(4)(N(3))(2)(MeOH)(2)](ClO(4))(2)·2MeOH (2), and [Ni(4)(L1)(4)(pyz)(2)(PhCOO)(2)(MeOH)(2)](ClO(4))(2)·7MeOH (3) (where HL and HL1 represent bipyridine-2-carboxamideoxime and pyrimidine-2-carboxamideoxime, respectively) are reported. Within the Ni(4)(2+) units of these compounds, distorted octahedral Ni(II) ions are bridged by carboxamideoximato ligands to adopt a distorted tetrahedral disposition. The Ni(4)(2+) unit, of C(2) symmetry, can also be viewed as a cube with single [O-atom] and double [NO oxime] bridging groups as atom edges, which define two almost square-planar Ni(O)(2)Ni rings and four irregular hexagonal Ni(NO)(2)Ni rings. To analyze the magnetic properties of 1-3, we have considered the simplest two-J model, where J(1) = J(2) (exchange interactions between the Ni(II) ions belonging to the Ni(O)(2)Ni square rings) and J(a) = J(b) = J(c) = J(d) (exchange interactions between the Ni(II) ions belonging to the Ni-(NO)(2)Ni hexagonal rings) with the Hamiltonian H = -J(1)(S(1)S(2) + S(3)S(4)) - J(a)(S(1)S(3) + S(1)S(4) + S(2)S(3) + S(2)S(4)). The J(1) and J(a) values derived from the fitting of the experimental susceptibility data are -5.8 cm(-1) and -22.1 cm(-1) for 1; -2.4 cm(-1) and -22.8 cm(-1) for 2, and +15.6 cm(-1) and -10.8 cm(-1) for 3. The magneto-structural results and density-functional theory (DFT) calculations demonstrate that the exchange interactions inside the Ni(μ-O)(2)Ni square rings depend on the Ni-O-Ni bridging angle (θ) and the out-of-plane angle of the NO oximate bridging group with respect to the Ni(O)(2)Ni plane (τ), whereas the interactions propagated through the Ni-N-O(Ni)-Ni exchange pathways defining the side of the hexagonal rings depend on the Ni-N-O-Ni torsion angle (α). In both cases, theoretical magneto-structural correlations were obtained, which allow the prediction of the angle for which ferromagnetic interactions are expected. For compound 3, the existence of the axial magnetic exchange pathway through the syn-syn benzoate bridge may also contribute (in addition to the θ and τ angles) to the observed F interaction in this compound through orbital countercomplementarity, which has been supported by DFT calculations. Finally, DFT calculations clearly show that the antiferromagnetic exchange increases when the dihedral angle between the O-Ni-O planes of the Ni(μ-O)(2)Ni square ring, β, increases.

Encapsulation of a magnesium hydroxide cubane by a bowl-shaped polypyrrolic Schiff base macrocycle.

Hydrolysis of a Pacman-shaped binuclear magnesium complex of a polypyrrolic Schiff base macrocycle results in the formation of a new magnesium hydroxide cubane that is encapsulated by the macrocyclic framework through both coordinative and hydrogen-bonding interactions.

Chiral single-molecule magnets: a partial Mn(III) supertetrahedron from achiral components

A [Mn(III)(9)] partial supertetrahedron is a Single-Molecule Magnet (SMM) with an energy barrier to magnetisation reversal of ~30 K and represents the first chiral SMM obtained from achiral starting materials.

Using the outer coordination sphere to tune the strength of metal extractants.

A series of 3-substituted salicylaldoximes has been used to demonstrate the importance of outer-sphere interactions on the efficacy of solvent extractants that are used to produce approximately one-quarter of the worlds copper. The distribution coefficient for extraction of copper by 5-tert-butyl-3-X-salicylaldoximes (X = H, Me, (t)Bu, NO(2), Cl, Br, OMe) varies by more than two orders of magnitude. X-ray structure determinations of preorganized free ligand dimers (10 new structures are reported) indicate that substituents with a hydrogen-bond acceptor atom attached to the 3-carbon atom, ortho to the phenolic oxygen, buttress the intermolecular hydrogen bond from the oximic proton. Density functional theory calculations demonstrate that this hydrogen-bond buttressing is maintained in copper(II) complexes and contributes significantly to their relative stabilities in energy-minimized gas-phase structures. A remarkable correlation between the order of the calculated enthalpies of formation of the copper complexes in the gas phase and the observed strength of the ligands as copper solvent extractants is ascribed to the low solvation energies of species in the water-immiscible phase and/or the similarities of the solvation enthalpies of the preorganized ligand dimers and their copper(II) complexes.

Donor-extended tripodal pyrroles: encapsulation, metallation, and H-bonded tautomers **

A tripodal iminopyrrole provides an environment suited to the encapsulation of water through hydrogen-bonding, and the formation of metal complexes by deprotonation and imine-pyrrole tautomerisation.

Transport of metal salts by zwitterionic ligands; simple but highly efficient salicylaldoxime extractants

Attaching dialkylaminomethyl arms to commercial phenolic oxime copper extractants yields reagents which transport base metal salts very efficiently by forming neutral 1:1 or 1:2 complexes with zwitterionic forms of the ligands.

Building Fe(III) clusters with derivatised salicylaldoximes

The syntheses, structures and magnetic properties of nine new iron complexes containing salicylaldoxime (saoH(2)) or derivatised salicylaldoximes (R-saoH(2)), [Fe(3)O(OMe)(Ph-sao)(2)Cl(2)(py)(3)].2MeOH (1.2MeOH), [Fe(3)O(OMe)(Ph-sao)(2)Br(2)(py)(3)].Et(2)O (2.Et(2)O), [Fe(4)(Ph-sao)(4)F(4)(py)(4)].1.5MeOH (3.1.5MeOH), [Fe(6)O(2)(OH)(2)(Et-sao)(2)(Et-saoH)(2)(O(2)CPh)(6)] (4), [HNEt(3)](2)[Fe(6)O(2)(OH)(2)(Et-sao)(4)(O(2)CPh(Me)(2))(6)].2MeCN (5.2MeCN), [Fe(6)O(2)(O(2)CPh)(10)(3-(t)But-5-NO(2)-sao)(2)(H(2)O)(2)].2MeCN (6.2MeCN), [Fe(6)O(2)(O(2)CCH(2)Ph)(10)(3-(t)But-sao)(2)(H(2)O)(2)].5MeCN (7.5MeCN), {[Fe(6)Na(3)O(OH)(4)(Me-sao)(6)(OMe)(3)(H(2)O)(3)(MeOH)(6)].MeOH}n (8.MeOH) and [HNEt(3)](2)[Fe(12)Na(4)O(2)(OH)(8)(sao)(12)(OMe)(6)(MeOH)(10)] (9) are discussed. The predominant building block appears to be the triangular [Fe(3)O(R-sao)(3)](+) species which can self-assemble into more elaborate arrays depending on reaction conditions. An interesting observation is that the R-saoH(-)/R-sao(2-) ligand system tends to adopt coordination modes similar to carboxylates. The most unusual molecule is the [Fe(4)F(4)] molecular square, 3. While Cl(-) and Br(-) appear to act only as terminal ligands, the F(-) ions bridge making a telling impact on molecular structure and topology.

Assembling molecular triangles into discrete and infinite architectures

Having established that molecules with general formulae [MnIII6O2(R-sao)6(O2CR)2(L)4–6] ([Mn6]) and [MnIII3O(R-sao)3(X)(L)3] ([Mn3]) (saoH2 = salicylaldoxime; R = H, Me, Et etc; X = RCO2−, ClO4−; L = solvent), with the latter being the analogous “half” molecules of the former, exhibit the phenomenon of single-molecule magnetism, we have exploited them as building blocks to construct supramolecular architectures by means of host–guest interactions and coordination driven self-assembly. A number of discrete and infinite architectures, namely [MnIII3O(Ph-sao)3(4Cl-sbz)3(MeOH)3]2(OH)(ClO4)·2MeOH (1·2MeOH), [MnIII3O(Ph-sao)3(4Me-sbz)3(EtOH)3]2(OH)(NO3) (2), {[MnIII3O(Et-sao)3(4,4′-bpy)2(MeOH)] ClO4·1.5MeOH·Et2O}n (3·1.5MeOH·Et2O), {[MnIII3O(sao)3(4,4′-bpe)1.5]ClO4·3MeOH}n (4·3MeOH) and [{MnIII3O(Et-sao)3(O2CPh)(EtOH)}2{4,4′-bpe}2] (5), based on the molecular triangle [Mn3] and various pyridyl-type ligands (4Cl-sbz = 4-chlorostilbazole, 4Me-sbz = 4-methylstilbazole, 4,4′-bpy = 4,4′-bipyridine and 4,4′-bpe = trans-1,2-bis(4-pyridyl)ethylene) were obtained and structurally and magnetically characterized.

Polyacidic multiloading metal extractants

Novel polynucleating, di- and tri-acidic ligands have been designed to increase the molar and mass transport efficiencies for the recovery of base metals by solvent extraction.

Structural, magnetic, and electronic properties of phenolic oxime complexes of Cu and Ni.

Square planar complexes of the type Ni(L(1))(2), Ni(L(2))(2), Cu(L(1))(2), and Cu(L(2))(2), where L(1)H = 2-hydroxy-5-t-octylacetophenone oxime and L(2)H = 2-hydroxy-5-n-propylacetophenone oxime, have been prepared and characterized by single-crystal X-ray diffraction, cyclic voltammetry, UV/vis spectroscopy, field-effect-transistor measurements, density functional theory (DFT) and time-dependent DFT (TDDFT) calculations, and, in the case of the paramagnetic species, electron paramagnetic resonance (EPR) and magnetic susceptibility. Variation of alkyl groups on the ligand from t-octyl to n-propyl enabled electronic isolation of the complexes in the crystal structures of M(L(1))(2) contrasting with π-stacking interactions for M(L(2))(2) (M = Ni, Cu). This was evidenced by a one-dimensional antiferromagnetic chain for Cu(L(2))(2) but ideal paramagnetic behavior for Cu(L(1))(2) down to 1.8 K. Despite isostructural single crystal structures for M(L(2))(2), thin-film X-ray diffraction and scanning electron microscopy (SEM) revealed different morphologies depending on the metal and the deposition method (vapor or solution). The Cu complexes displayed limited electronic interaction between the central metal and the delocalized ligands, with more mixing in the case of Ni(II), as shown by electrochemistry and UV/vis spectroscopy. The complexes M(L(2))(2) showed poor charge transport in a field-effect transistor (FET) device despite the ability to form π-stacking structures, and this provides design insights for metal complexes to be used in conductive thin-film devices.