Direct Electrochemical Investigations of 17-Electron Complexes of CpM(CO)(3)(*) (M = Mo, W, and Cr)

Photolysis of complexes of the type M(2)(CO)(6)(RC(5)H(4))(2) (where M = W, Mo, Cr and R = H (Cp) or CH(3) (Cp')) leads to the production of short lived 17-electron radicals. Direct electrochemical characterization of these intermediates has been achieved using a technique known as photomodulated voltammetry (PMV). The results from PMV analysis are in excellent agreement with literature estimates for CpMo(CO)(3)(*) and CpCr(CO)(3)(*). However, CpW(CO)(3)(*) is found to be shifted oxidatively 115 mV relative to previous literature estimates. The change in the value for the tungsten complex changes previous estimates to the bond dissociation energy for tungsten metal hydrides by 3.0 +/- 0.9 kcal/mol. Lifetime information on the radicals is also reported based on the phase shift of the electrochemical signal observed by PMV under limiting current conditions.     

A TD-DFT study of the absorption spectra of fast dye salts

The UV/visible spectra of a series of diazonium fast dyes have been evaluated by using a time-dependent density functional theory approach explicitly taking into account bulk solvation effects. Using the PBE0 functional with the 6-311G(2d,2p) atomic basis set, the agreement between theory and experiment is excellent for these cationic species. The effects on the spectra of chemical substitution are analysed.     

Thermally Activated Delayed Fluorescence in a Y3N@C80 Endohedral Fullerene: Time‐Resolved Luminescence and EPR Studies

The endohedral fullerene Y₃N@C₈₀ exhibits luminescence with reasonable quantum yield and extraordinary long lifetime. By variable‐temperature steady‐state and time‐resolved luminescence spectroscopy, it is demonstrated that above 60 K the Y₃N@C₈₀ exhibits thermally activated delayed fluorescence with maximum emission at 120 K and a negligible prompt fluorescence. Below 60 K, a phosphorescence with a lifetime of 192±1 ms is observed. Spin distribution and dynamics in the triplet excited state is investigated with X‐ and W‐band EPR and ENDOR spectroscopies and DFT computations. Finally, electroluminescence of the Y₃N@C₈₀/PFO film is demonstrated opening the possibility for red‐emitting fullerene‐based organic light‐emitting diodes (OLEDs).     

A Planar‐Chiral Rhodium(III) Catalyst with a Sterically Demanding Cyclopentadienyl Ligand and Its Application in the Enantioselective Synthesis of Dihydroisoquinolones

The rapid development of enantioselective C?H activation reactions has created a demand for new types of catalysts. Herein, we report the synthesis of a novel planar‐chiral rhodium catalyst [(C₅H₂^tBu₂CH₂^tBu)RhI₂]₂ in two steps from commercially available [(cod)RhCl]₂ and tert‐butylacetylene. Pure enantiomers of the catalyst were obtained through separation of its diastereomeric adducts with natural (S)‐proline. The catalyst promoted enantioselective reactions of aryl hydroxamic acids with strained alkenes to give dihydroisoquinolones in high yields (up to 97 %) and with good stereoselectivity (up to 95 % ee).     

Phase glass is a Bose metal: a new conducting state in two dimensions

In the quantum rotor model with random exchange interactions having a nonzero mean, three phases, a (i) phase (Bose) glass, (ii) superfluid, and (iii) Mott insulator, meet at a bicritical point. We demonstrate that proximity to the bicritical point and the coupling between the energy landscape and the dissipative degrees of freedom of the phase glass lead to a metallic state at T = 0. Consequently, the phase glass is unique in that it represents a concrete example of a metallic state that is mediated by disorder, even in 2D. We propose that the experimentally observed metallic phase which intervenes between the insulator and the superconductor in a wide range of thin films is in actuality a phase glass.     

Cover Picture

The cover picture shows, on the lip of Oncidium tigrinum La Llave et Lex., the superposition of beta-ionone and a tailor-made bicyclo[6.4.0]dodecene. The structural similarity of the two molecules accounts for their close odors. beta-Ionone is present in the scent of the depicted tropical orchid at the unusually high level of 14.5 %. An overview of the olfactory spectrum is shown in the background. More on scents and their molecules can be found in the review of P. Kraft et al. on p. 2980 ff.     

BRS Cohomology and the Chern Character in Noncommutative Geometry

We briefly report on new results concerning a perturbation expansion structure within the framework of an analytic version of perturbative quantum chromodynamics (pQCD). This approach combines the RG symmetry with the Källén–Lehmann analyticity in the Q² variable. The procedure of analytization matches this analyticity with the RG invariance by adding to the analytized invariant coupling some nonperturbative contributions containing no adjustable parameters. In turn, the new perturbative expansion (the APT expansion) for an observable represents asymptotic expansion over a nonpower set of specific functions rather than in powers of . We analyze this set and show that it obeys different properties in various ranges of the Q² variable. In the UV, it is close to the power set used in the pQCD calculation. However, generally, this set is of a more complicated nature. In the low Q² region the behavior of is oscillating. Here, the APT expansion has a feature of asymptotic expansion à la Erdélyi. The issue of the consistency of an analytization procedure with the RG structure of observables is also discussed.     

New synthetic routes to vinyl sulfides,ketene thioacetals and their seleno analogues from carbonyl compounds

Title compounds have been prepared from carbonyl compounds by formal removal of hydroxyl and sulfenyl or hydroxyl and selenyl moieties from the corresponding functionalized β-hydroxysulfides or β-hydroxyselenides.