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Nickel plays an important role in areas as diverse as metallurgy, magnetism and biology as well as in chemical applications such as the catalytic transformation of organic substrates. Despite nickel's importance, the investigation of its compounds in various oxidation states remains uneven and those in the +1 oxidation are less common than those in the neighboring 0 and +2 oxidation states. Nonetheless, in recent years, the volume of work on Ni(i) complexes has increased to the extent that they can be no longer regarded as rare. This review focuses on the syntheses and structures of Ni(i) complexes and shows that they display a range of structures, reactivity and magnetic behavior that places them in the forefront of current nickel chemistry research.

A series of high spin, two-coordinate first row transition metal-amido complexes, M{N(SiMe3)Dipp}2 {M = Fe (1), Co (2), or Ni (3); Dipp = C6H3-2,6-Pr(i)2} and a tetranuclear C-H activated chromium amide, [Cr{N(SiMe2CH2)Dipp}2Cr]2(THF) (4), were synthesized by reaction of their respective metal dihalides with 2 equiv of the lithium amide salt. They were characterized by X-ray crystallography, electronic and infrared spectroscopy, SQUID magnetic measurements, and computational methods. Contrary to steric considerations, the structures of 1-3 display planar eclipsed M{NSiC(ipso)}2 arrays and short M-N distances. DFT calculations, corrected for dispersion effects, show that dispersion interactions involving C-H-H-C moieties likely stabilize the structures by 21.1-29.4 kcal mol(-1), depending on the level of the calculations employed. SQUID measurements confirm high spin electron configurations for all the complexes and substantial orbital contributions for 1 and 2.

Syntheses and characterizations are reported for dimolybdenum(II) compounds supported by the diarylformamidinate (ArNC(H)NAr(-)) ligand, where Ar is XC(6)H(4)(-), with X as p-OMe (1), H (2), m-OMe (3), p-Cl (4), m-Cl (5), m-CF(3) (6), p-COMe (7), p-CF(3) (8), or Ar is 3,4-Cl(2)C(6)H(3)(-) (9) or 3,5-Cl(2)C(6)H(3)(-) (10). The (quasi)reversible oxidation potentials measured for the Mo(2)(5+)/Mo(2)(4+) couple were found to correlate with the Hammett constant (sigma(X)) of the aryl substituents according to the following equation: DeltaE(1/2) = E(1/2)(X) - E(1/2)(H) = 87(8sigma(X)) mV. Molecular structure determinations of compounds 1, 2, 5, and 10 revealed an invariant core geometry around the Mo(2) center, with statistically identical Mo-Mo quadruple bond lengths of 2.0964(5), 2.0949[8], 2.0958(6), and 2.0965(5) Å, respectively. Magnetic anisotropies for compounds 1-10 estimated on the basis of (1)H NMR data were similar and unrelated to sigma(X). Similarity in UV-vis spectra was also found within the series, which, in conjunction with the features of both molecular structures and (1)H NMR spectra, was interpreted as the existence of a constant upper valence structure across the series. Results of Fenske-Hall calculations performed for several model compounds paralleled the experimental observations.

Within the broad field called ''supramolecular chemistry,'' there is a sector that is based on the use of metal atoms or ions as key elements in promoting the assembly and dictating the main structural features of the supramolecular products. Considerable success has been achieved by using MOM bonded dimetal entities in this role. Metal-metal bonded cationic complexes of the [M2(DAniF)n(MeCN)8-2n] (4؊n)؉ type, where M ‫؍‬ Mo or Rh and DAniF is an N,N -di-p-anisylformamidinate anion, have been used as subunit precursors and then linked by various equatorial and axial bridging groups such as polycarboxylate anions, polypyridyls, and polynitriles. Characterization of the products by single-crystal x-ray diffraction, cyclic voltammetry, differential pulse voltammetry, NMR, and other spectroscopic techniques has revealed the presence of discrete tetranuclear (pairs or loops), hexanuclear (triangles), octanuclear (squares), and dodecanuclear (cages) species and one-, two-, or three-dimensional molecular nanotubes. These compounds display a rich electrochemical behavior that is affected by the nature of the linkers.T he literature on what is called ''supramolecular chemistry'' has grown at an extraordinary rate in the last two decades, since the term was introduced. The term can be described, with no disrespect, as one of the most spectacularly successful buzz words of our time, along with a few others such as molecular engineering, molecular wires, self-assembly, and nanoanything-you-can-think-of. Our laboratory has unabashedly joined the army of those already in the field of supramolecular chemistry. There appear to be three main branches of supramolecular chemistry: one in which hydrogen bonding plays the key role, another in which various other socalled ''noncovalent interactions,'' such as stacking of aromatic rings, are the main features, and a third in which coordination of ligands to metal ions is the central idea. It is the third of these branches to which the work summarized here belongs.Just one more introductory remark seems appropriate before entering into specifics. The idea of putting ligand-to-metal bonds in the same category with hydrogen bonds and other weak noncovalent bonds seems to be little more than a misapprehension on the part of people not previously familiar with coordination chemistry. There is, in general, nothing weak or ''noncovalent'' about metal-ligand bonds, bond energies of up to 50 kcal mol Ϫ1 being quite normal and, although naturally they are polar, they are also appreciably covalent.Beginning in early 1998 in this laboratory, the use of dimetal units (e.g., Mo 2 4ϩ and Rh 2 4ϩ ) to build supramolecular arrays has been pioneered. Although this field is still young, its basic outlines have been established, and other chemists are beginning to contribute to it. We have used dimetal units for five major reasons: (i) Dimetal units can be used to create neutral rather than highly positive oligomers and networks, which can then be oxidized in a controlled way, with retention of structura...

A review work is done for the electronic and optical properties of graphene nanoribbons in magnetic, electric, composite, and modulated fields. Effects due to the lateral confinement, curvature, stacking, non-uniform subsystems and hybrid structures are taken into account. The special electronic properties, induced by complex competitions between external fields and geometric structures, include many one-dimensional parabolic subbands, standing waves, peculiar edge-localized states, width- and field-dependent energy gaps, magnetic-quantized quasi-Landau levels, curvature-induced oscillating Landau subbands, crossings and anti-crossings of quasi-Landau levels, coexistence and combination of energy spectra in layered structures, and various peak structures in the density of states. There exist diverse absorption spectra and different selection rules, covering edge-dependent selection rules, magneto-optical selection rule, splitting of the Landau absorption peaks, intragroup and intergroup Landau transitions, as well as coexistence of monolayer-like and bilayer-like Landau absorption spectra. Detailed comparisons are made between the theoretical calculations and experimental measurements. The predicted results, the parabolic subbands, edge-localized states, gap opening and modulation, and spatial distribution of Landau subbands, have been identified by various experimental measurements.

Three potassium crown ether salts, [K(Et2O)2(18-crown-6)][Fe{N(SiMe3)Dipp}2] (1a; Dipp = C6H3-2,6-Pr(i)2), [K(18-crown-6)][Fe{N(SiMe3)Dipp}2]·0.5PhMe (1b), and [K(18-crown-6)][M{N(SiMe3)Dipp}2] (M = Co, 2; M = Ni, 3), of the two-coordinate linear or near-linear bis-amido monoanions [M{N(SiMe3)Dipp}2](-) (M = Fe, Co, Ni) were synthesized by one-electron reduction of the neutral precursors M{N(SiMe3)Dipp}2 with KC8 in the presence of 18-crown-6. They were characterized by X-ray crystallography, UV-vis spectroscopy, cyclic voltammetry, and magnetic measurements. The anions feature lengthened M-N bonds in comparison with their neutral precursors, with slightly bent coordination (N-Fe-N = ca. 172°) for the iron(I) complex, but linear coordination for the cobalt(I) and nickel(I) complexes. Fits of the temperature dependence of χMT of 1 and 2 reveal that the iron(I) and cobalt(I) complexes have large negative D zero-field splittings and a substantial orbital contribution to their magnetic moments with L = 2, whereas the nickel(I) complex has at most a small orbital contribution to its magnetic moment. The magnetic results have been used to propose an ordering of the 3d orbitals in each of the complexes.

This article reviews the rich magneto-electronic properties of multilayer graphene systems. Multilayer graphenes are built from graphene sheets attracting one another by van der Waals forces; the magneto-electronic properties are diversified by the number of layers and the stacking configurations. For an N-layer system, Landau levels are divided into N groups, with each identified by a dominant sublattice associated with the stacking configuration. We focus on the main characteristics of Landau levels, including the degeneracy, wave functions, quantum numbers, onset energies, field-dependent energy spectra, semiconductor-metal transitions, and crossing patterns, which are reflected in the magneto-optical spectroscopy, scanning tunneling spectroscopy, and quantum transport experiments. The Landau levels in AA-stacked graphene are responsible for multiple Dirac cones, while in AB-stacked graphene the Dirac properties depend on the number of graphene layers, and in ABC-stacked graphene the low-lying levels are related to surface states. The Landau-level mixing leads to anticrossings patterns in energy spectra, which are seen for intergroup Landau levels in AB-stacked graphene, while in particular, a formation of both intergroup and intragroup anticrossings is observed in ABC-stacked graphene. The aforementioned magneto-electronic properties lead to diverse optical spectra, plasma spectra, and transport properties when the stacking order and the number of layers are varied. The calculations are in agreement with optical and transport experiments, and novel features that have not yet been verified experimentally are presented.