Synthesis of luminescent gold(I) and gold(III) complexes with a triphosphine ligand

We have synthesized and characterized a series of trinuclear gold(I) complexes [(AuX)(3)(mu-triphos)] (triphos = bis(2-diphenylphosphinoethyl)phenylphosphine; X = Cl 1, Br 2, I 3, C(6)F(5) 4) and di- and trinuclear gold(III) complexes [[Au(C(6)F(5))(3)](n)(mu-triphos)] (n = 2 (5), 3 (6)). The crystal structure of 6 [[Au(C(6)F(5))(3)](3)(mu-triphos)] has been determined by X-ray diffraction studies, which show the triphosphine in a conformation resulting in very long gold-gold distances, probably associated with the steric requirements of the tris(pentafluorophenyl)gold(III) units. Complex 6 crystallizes in the triclinic space group P(-1) with a = 12.7746(16) A, b = 18.560(2) A, c = 21.750(3) A, alpha = 98.215(3) degrees, beta = 101.666(3) degrees, gamma = 96.640(3) degrees, and Z = 2. Chloride substitutions in complex 1 afford trinuclear gold(I) complexes [(AuX)(3)(mu-triphos)] (X = Fmes (1,3,5-tris(trifluoromethyl)phenyl) 7, p-SC(6)H(4)Me 8, SCN 9) and [Au(3)Cl(3)(-)(n)()(S(2)CNR(2))(n)(mu-triphos)] (R = Me, n = 3 (10), 2 (12), 1 (14); R = CH(2)Ph, n = 3 (11), 2 (13), 1 (15)). The luminescence properties of these complexes in the solid state have been studied; at low temperature most of them are luminescent, including the gold(III) derivative 6, with the intensity and the emission maxima being clearly influenced by the nature and the number of the ligands bonded to the gold centers.     

Preparation of pentahalophenyl p-tolylisocyanide complexes of gold(I) and their reactions with amines,ammonia and alcohols

(Pentahalophenyl) (p-tolylisocyanide)gold(I) complexes were prepared by treating Au(C₆X₅) (tetrahydrothiophen) (X = F, Cl or Br) with p-MeC₆H₄NC. Their reactivity toward nucleophiles was studied and found to decrease in the sequence: primary amines > ammonia > secondary amines > aromatic amines > alcohols; the effects of the various C₆X₅ groups were less pronounced, but decreased according to C₆F₅ > C₆Cl₅ > C₆Br₅.Twenty-five novel gold(I) carbene derivatives were isolated.     

Selenolate gold complexes with aurophilic Au(I)-Au(I) and Au(I)-Au(III) interactions

The gold(I) selenolate compound [Au(2)(SePh)(2)(mu-dppf)] (dppf = 1,1'-bis(diphenylphosphino)ferrocene) has been prepared by reaction of [Au(2)Cl(2)(mu-dppf)] with PhSeSiMe(3) in a molar ratio 1:2. This complex reacts with gold(I) or gold(III) derivatives to give polynuclear gold(I)-gold(I) or gold(I)-gold(III) complexes of the type [Au(4)(mu-SePh)(2)(PPh(3))(2)(mu-dppf)](OTf)(2), [Au(3)(C(6)F(5))(3)(mu-SePh)(2)(mu-dppf)], or [Au(4)(C(6)F(5))(6)(mu-SePh)(2)(mu-dppf)], with bridging selenolate ligands. The reaction of [Au(2)(SePh)(2)(mu-dppf)] with 1 equiv of AgOTf leads to the formation of the insoluble Ag(SePh) and the compound [Au(2)(mu-SePh)(mu-dppf)]OTf. The complexes [Au(4)(C(6)F(5))(6)(mu-SePh)(2)(mu-dppf)] and [Au(2)(mu-SePh)(mu-dppf)]OTf (two different solvates) have been characterized by X-ray diffraction studies and show the presence of weak gold(I)-gold(III) interactions in the former and intra- and intermolecular gold(I)-gold(I) inter-actions in the later.     

Tabu search with strategic oscillation for the maximally diverse grouping problem

We propose new heuristic procedures for the maximally diverse grouping problem (MDGP). This NP-hard problem consists of forming maximally diverse groups—of equal or different size—from a given set of elements. The most general formulation, which we address, allows for the size of each group to fall within specified limits. The MDGP has applications in academics, such as creating diverse teams of students, or in training settings where it may be desired to create groups that are as diverse as possible. Search mechanisms, based on the tabu search methodology, are developed for the MDGP, including a strategic oscillation that enables search paths to cross a feasibility boundary. We evaluate construction and improvement mechanisms to configure a solution procedure that is then compared to state-of-the-art solvers for the MDGP. Extensive computational experiments with medium and large instances show the advantages of a solution method that includes strategic oscillation.     

Measuring localization-delocalization phenomena in a quantum corral

The standard deviations and Shannon information entropies of the probability densities for a particle in a quantum corral are compared and contrasted to determine their effectiveness in measuring particle (de)localization. We illustrate how the two measures emphasize different aspects of the underlying distributions which can lead to inconsistent interpretations. Among these, we show that the Shannon entropy is able to distinguish between the presence of an attractive or repulsive effective potential in the radial Schrödinger equation while the standard deviation does not. The analysis of this radial model is then extended to momentum space where the dependence of the measures, entropic sum and uncertainty product on the effective potential, is examined.     

Intercommutation of semilocal strings and Skyrmions

We study the intercommuting of semilocal strings and Skyrmions for a wide range of internal parameters, velocities, and intersection angles by numerically evolving the equations of motion. We find that the collisions of strings and strings, strings and Skyrmions, and Skyrmions and Skyrmions all lead to intercommuting for a wide range of parameters. Even the collisions of unstable Skyrmions and strings lead to intercommuting, demonstrating that the phenomenon of intercommuting is very robust, extending to dissimilar field configurations that are not stationary solutions. Even more remarkably, at least for the semilocal U(2) formulation considered here, all intercommutations trigger a reversion to Nielsen-Olesen strings.     

Photon channelling in foams

Experiments by Gittings, Bandyopadhyay and Durian (Europhys. Lett. 65, 414 (2004)) demonstrate that light possesses a higher probability to propagate in the liquid phase of a foam due to total reflection. The authors term this observation photon channelling which we investigate in this article theoretically. We first derive a central relation in the work of Gitting et al. without any free parameters. It links the photon's path-length fraction f in the liquid phase to the liquid fraction ɛ. We then construct two-dimensional Voronoi foams, replace the cell edges by channels to represent the liquid films and simulate photon paths according to the laws of ray optics using transmission and reflection coefficients from Fresnel's formulas. In an exact honeycomb foam, the photons show superdiffusive behavior. It becomes diffusive as soon as disorder is introduced into the foams. The dependence of the diffusion constant on channel width and refractive index is explained by a one-dimensional random-walk model. It contains a photon channelling state that is crucial for the understanding of the numerical results. At the end, we shortly comment on the observation that photon channelling only occurs in a finite range of ɛ.     

(Tl[Au(C(6)Cl(5))(2)])(n): A vapochromic complex

The X-ray structure of (Tl[Au(C(6)Cl(5))(2)])(n), 1, consists of 1-D linear polymer chains parallel to the crystallographic z axis. The crystal structure of 1 has channels that run parallel to these chains with interatom distances in the range 3.231-4.076 A. There are holes in these channels with diameters as large as 10.471 A, which can accommodate a variety of solvents. Complex 1 displays reversible vapochromic emission and absorption spectral behavior when the solid is exposed to a variety of organic vapors such as acetone, acetonitrile, triethylamine, acetylacetone, tetrahydrothiophene, 2-fluoropyridine, tetrahydrofuran, and pyridine. Complex 1 is luminescent at room temperature and at 77 K in the solid state. UV excitation at 495 nm leads to an emission at 531 nm.