High-nuclearity close-packed palladium-nickel carbonyl phosphine clusters: heteropalladium.

[Pd(16)Ni(4)(CO)(22)(PPh(3))(4)](2)(-) (1) and [Pd(33)Ni(9)(CO)(41)(PPh(3))(6)](4)(-) (2) were obtained as the two major products from the reduction of PdCl(2)(PPh(3))(2) with [Ni(6)(CO)(12)](2)(-). Their crystal structures as [PPh(4)](+) salts were unambiguously determined from CCD X-ray crystallographic analyses; the resulting stoichiometries were ascertained from elemental analyses. Infrared, multinuclear (1)H, (31)P[(1)H] NMR, UV-vis, CV, variable-temperature magnetic susceptibility, and ESI FT/ICR mass spectrometric measurements were performed. The Pd(16)Ni(4) core of 1 ideally conforms to a ccp nu(3) tetrahedron of pseudo-T(d)() (4 3m) symmetry. Its geometry normal to each tetrahedral Pd(7)Ni(3) face (i.e., along each of the four 3-fold axes) may be viewed as a four-layer stacking of 20 metal atoms in a ccp [a(Ni(1)) b(Pd(3)) c(Pd(6)) a(Pd(7)Ni(3))] sequence. A comparative analysis of the different ligand connectivities about the analogous metal-core geometries in 1 and the previously reported [Os(20)(CO)(40)](2)(-) has stereochemical implications pertaining to the different possible modes of carbon monoxide attachment to ccp metal(111) surfaces. The unique geometry of the Pd(33)Ni(9) core of 2, which has pseudo-D(3)(h)() (6 2m) symmetry, consists of five equilateral triangular layers that are stacked in a hcp [a(Pd(7)Ni(3)) b(Pd(6)) a(Pd(7)Ni(3)) b(Pd(6)) a(Pd(7)Ni(3))] sequence. Variable-temperature magnetic susceptibility measurements indicated both 1 and 2 to be diamagnetic over the entire temperature range from 5.0 to 300 K. Neutral Pd(12)(CO)(12)(PPh(3))(6) (3) and [Pd(29)(CO)(28)(PPh(3))(7)](2)(-) (4) as the [PPh(4)](+) salt were obtained as minor decomposition products from protonation reactions of 1 and 2, respectively, with acetic acid. Compound 3 of pseudo-D(3)(d)() (3 2/m) symmetry represents the second highly deformed hexacapped octahedral member of the previously established homopalladium family of clusters containing uncapped, monocapped, bicapped, and tetracapped Pd(6) octahedra. The unprecedented centered 28-atom polyhedron for the Pd(29) core of 4 of pseudo-C(3)(v)() (3m) symmetry may be described as a four-layer stacking of 29 metal atoms in a mixed hcp/ccp [a(Pd(1)) b(Pd(3)) a(Pd(10)) c(Pd(15))] sequence.

1-D and 2-D homoleptic dicyanamide structures, [Ph4P]2[CoII[N(CN)2]4] and [Ph4P][M[N(CN)2]3] (M = Mn, Co).

The homoleptic complexes [Ph(4)P](2)[Co[N(CN)(2)](4)] and [Ph(4)P][M[N(CN)(2)](3)] [M = Co, Mn] have been structurally as well as magnetically characterized. The complexes containing [M[N(CN)(2)](4)](2-) form 1-D chains, which are bridged via a common dicyanamide ligand in [M[N(CN)(2)](3)](-) to form a 2-D structure. The five-atom [NCNCN](-) bridging ligands lead to weak magnetic coupling along a chain. The six [NCNCN](-) ligands lead to a (4)T(1g) ground state for Co(II) which has an unquenched spin-orbit coupling that is reflected in the magnetic properties. Long-range magnetic ordering was not observed in any of these materials.

Field-induced metal-insulator transition in a two-dimensional organic superconductor.

The quasi-two-dimensional organic superconductor beta"-(BEDT-TTF)2SF5CH2CF2SO3 (Tc approximately 4.4 K) shows very strong Shubnikov-de Haas (SdH) oscillations which are superimposed on a highly anomalous steady background magnetoresistance, Rb. Comparison with de Haas-van Alphen oscillations allows a reliable estimate of Rb which is crucial for the correct extraction of the SdH signal. At low temperatures and high magnetic fields insulating behavior evolves. The magnetoresistance data violate Kohler's rule, i.e., cannot be described within the framework of semiclassical transport theory, but converge onto a universal curve appropriate for dynamical scaling at a metal-insulator transition.

Organic superconductors--new benchmarks.

Recent advances in the design and synthesis of organic synthetic metals have yielded materials that have the highest superconducting transition temperatures (T(c) approximately 13 kelvin) reported for these systems. These materials have crystal structures consisting of alternating layers of organic donor molecules and inorganic anions. Organic superconductors have various electronic and magnetic properties and crystal structures that are similar to those of the inorganic copper oxide superconductors (which have high T(c) values); these similarities include highly anisotropic conductivities, critical fields, and short coherence lengths. The largest number of organic superconductors, including those with the highest T(c) values, are charge-transfer salts derived from the electron donor molecule BEDT-TTF or ET [bis(ethylenedithio)-tetrathiafulvalene]. The synthesis and crystal structures of these salts are discussed; their electrical, magnetic, and band electronic structure properties and their many similarities to the copper oxide superconductors are treated as well.