Gordon T. Yee

A Room-Temperature Molecular/Organic-Based Magnet

The reaction of bis(benzene)vanadium with tetracyanoethylene, TCNE, affords an insoluble amorphous black solid that exhibits field-dependent magnetization and hysteresis at room temperature. The critical temperature could not be estimated as it exceeds 350 kelvin, the thermal decomposition temperature of the sample. The empirical composition of the reported material is V(TCNE)x�Y(CH2Cl2) with x ∼ 2 and Y ∼ 1/2. On the basis of the available magnetic and infrared data, threedimensional antiferromagnetic exchange of the donor and acceptor spins resulting in ferrimagnetic behavior appears to be the mode of magnetic coupling.

Gd3N@C84(OH)x: a new egg-shaped metallofullerene magnetic resonance imaging contrast agent.

Water-soluble derivatives of gadolinium-containing metallofullerenes have been considered to be excellent candidates for new magnetic resonance imaging (MRI) contrast agents because of their high relaxivity and characteristic encapsulation of the lanthanide ions (Gd(3+)), preventing their release into the bioenvironment. The trimetallic nitride template endohedral metallofullerenes (TNT EMFs) have further advantages of high stability, high relative yield, and encapsulation of three Gd(3+) ions per molecule as illustrated by the previously reported nearly spherical, Gd3N@I(h)-C80. In this study, we report the preparation and functionalization of a lower-symmetry EMF, Gd3N@C(s)-C84, with a pentalene (fused pentagons) motif and an egg-shaped structure. The Gd3N@C84 derivative exhibits a higher (1)H MR relaxivity compared to that of the Gd3N@C80 derivative synthesized the same way, at low (0.47 T), medium (1.4 T), and high (9.4 T) magnetic fields. The Gd3N@C(s)-C84 derivative exhibits a higher hydroxyl content and aggregate size, as confirmed by X-ray photoelectron spectroscopy (XPS) and dynamic light scattering (DLS) experiments, which could be the main reasons for the higher relaxivity.

A cyano-based octanuclear {Fe(III)(4)Ni(II)(4)} single-molecule magnet.

A new low symmetry octanuclear cyano-based {Fe(III)(4)Ni(II)(4)} single-molecule magnet (SMM) is described. This SMM exhibits the highest energy barrier (Delta/k(B) approximately 33 K) for magnetization reversal seen for any first-row cyanide-based complex. The importance of anisotropy axes alignment and their impact on SMM properties are illustrated when cubic {Fe(III)(4)Ni(II)(4)} boxes are compared to octanuclear complexes of lower overall symmetry.

Solid-state spin crossover of Ni(II) in a bioinspired N3S2 ligand field.

The complex Tp(Ph,Me)NiS(2)CNMe(2) [Tp(Ph,Me) = hydrotris(3-phenyl-5-methyl-1-pyrazolyl)borate] features a bioinspired N(3)S(2) ligand set supporting a five-coordinate, trigonally distorted square-pyramidal geometry in the solid state. Spin crossover of Ni(II) was demonstrated by temperature-dependent X-ray crystallography and magnetic susceptibility measurements. The crystal lattice contains two independent molecules (i.e., Ni1 and Ni2). At 293 K, the observed bond lengths and susceptibility are consistent with high-spin (S = 1) Ni(II), and both molecules exhibit relatively short axial Ni-N bonds and long Ni-N and Ni-S equatorial bonds. At 123 K, the Ni1 complex remains high-spin, but the Ni2 molecule substantially crosses to a structurally distinct diamagnetic (S = 0) state with significant elongation of the axial Ni-N bond and offsetting contraction of the equatorial bonds. The temperature-dependent susceptibility data were fit to a spin equilibrium at Ni2 [ΔH° = 1.13(2) kcal/mol and ΔS° = +7.3(1) cal mol(-1) K(-1)] consistent with weak coupling to lattice effects. Cooling below 100 K results in crossover of the Ni1 complex.

Strong ferromagnetic metal–ligand exchange in a nickel bis(3,5-dipyridylverdazyl) complex

A new 1,5-dipyridyl verdazyl, synthesized from the corresponding dipyridyl hydrazone, coordinates nickel(ii) to form a structurally characterized, pseudooctahedral complex analogous to Ni(terpy)(2)(2+). The unusually short Ni-verdazyl distance results in strong ferromagnetic exchange (J(Ni-rad) = +300, J(rad-rad) = +160 cm(-1)) between all three paramagnetic species along with a metal-ligand charge transfer band in the electronic spectrum.

Antiferromagnetic coupling across a tetrametallic unit through noncovalent interactions

Three paramagnetic heterobimetallic lantern complexes of the form [PtM(tba)4(OH2)] (M = Fe, 1; Co, 2; Ni, 3; tba = thiobenzoate) have been prepared in a single-step, bench-top procedure. In all three cases, a lantern structure with Pt–M bonding is observed in solution and in the solid state. Compound 1 is a monomer whereas 3 exists as a dimer in the solid state via a Pt⋯Pt metallophilic interaction. Compound 2 has been characterized in forms with (2a, purple) and without (2b, yellow) Pt⋯Pt metallophilic interactions. The dimers 2a (J = −10 cm−1, based on the spin Hamiltonian Ĥ = −2J(SA·SB)) and 3 (J = −60 cm−1) exhibit antiferromagnetic coupling between the two first-row metal ions in the solid state via a Pt⋯Pt non-covalent metallophilic interaction. The electronic structure of C4v [PtM(tba)4], C2 [PtM(tba)4(OH2)], (M = Fe, Co, Ni) and D2 symmetry [PtM(tba)4(OH2)]2 M = Co, Ni, units have been studied with DFT calculations, confirming the relative spin-state energies observed and the antiferromagnetic exchange pathway through four dz2 orbitals. The compounds 2a and 3 are the first examples of antiferromagnetic coupling through an unbridged M⋯M contact.

Raman spectra of YBa2Cu3Ox superconductors with different oxygen content

The Raman spectra of high-purity samples of YBa/sub 2/Cu/sub 3/O/sub x/ were studied as a function of oxygen content 6

Novel co-operative magnetic properties of decamethylmanganocenium 2,3-dichloro-5,6-dicyanobenzoquinoneide, 3[Mn(C5Me5)2]:+[DDQ]˙–

The electron-transfer salt 3[Mn(C5Me5)2]:+[DDQ]˙–, isomorphous to orthorhombic [Fe(C5Me5)2]˙+[DDQ]˙–, has been prepared. It exhibits a complex field-dependent magnetic pahse diagram at low temperatures with evidence for ferromagnetic coupling as well as a low moment state below 4 K for zero-field cooled samples.

Optical and conductive properties of pyrazine-bridged iron, ruthenium and osmium octaethylporphyrin coordination polymers

Abstract The optical and conductive properties of neutral and partially oxidized pyrazine-bridged polymers of iron, ruthenium and osmium octaethylporphyrin are reported. Analogies between these systems and the Creutz-Taube mixed valence dimers are drawn. Analysis of the infrared spectra of the neutral polymers establishes a lower limit for the polymer chain lengths. Examination of a broad transition that develops in the infrared upon partial oxidation of these polymers offers insight into the degree of delocalization of the conduction electrons, which is found to increase on descending the iron triad. Varying the degree of oxidation affects both the features of this broad transition and the d.c. conductivities.

New Magnetically Coupled Bimetallic Complexes as Potential Building Blocks for Magnetic Materials

Long-lived organic cation radical species, [1I]−and [2I]−, are formed when bimetallic CoIII or VV(O) complexes of a new binucleating ligand are oxidized by one electron. The VV(O) complex, [2I]−, has a total spin, ST, of 1/2, while the robust CoIII complex, [1I]−, has ST=3/2. The figure shows the spin arrangement within the complexes as deduced from combined EPR and SQUID measurements. The ferrimagnetic system, [1I]−, has both CoIII spin centers aligned in a common direction, an important step towards building ferromagnetic or ferrimagnetic network solids.