Induced Correspondence of a Local π‐Aromatic Sextet in Heteroannulenes: Synthesis and Characterization

Acid‐catalyzed [3+3] condensation reactions of two hitherto unknown tripyrrane moieties with pentafluorobenzaldehyde has led to the formation of new generation heteroannulene (4.1.4.1) and mutant heteroannulene (1.1.1.1.1.1). Inclusion of local π‐aromatic sextets, namely the N‐methyl pyrrole rings through β,β‐linkages and α,β‐linkages, has led to the isolation of first ever heteroannulenes cross‐conjugated at four points and two points respectively within the macrocycles.     

Polymer‐supported palladium: A hybrid system for multifunctional catalytic application

Polymer‐supported palladium was synthesized by applying a single‐step wet chemical synthesis route and the resultant composite material was characterized by means of various techniques. Infrared and UV–visible spectra provided information on the chemical structure of the polymer. Microscopy techniques showed the general morphology of the polymer. The oxidation state of palladium was determined using the X‐ray photoelectron spectroscopy method. The synthesized material was applied as a heterogeneous catalyst for the Heck coupling reaction and also as an electrocatalyst for the oxidation of cysteine.     

Kinetics and Mechanism of the Ligand Substitution Reaction of the Di-<Emphasis Type="Italic">μ</Emphasis>-hydroxobis(bipyridyl)dipalladium(II) Ion with some Bio-relevant Ligands

The interaction of di-μ-hydroxobis(bipyridyl)dipalladium(II) with the selected bio-relevant ligands: thioglycolic acid (HL¹), glutathione(HL²) and DL-penicillamine(HL³) has been studied spectrophotometrically in aqueous medium as a function of complex and ligand concentrations, pH, and temperature at constant ionic strength. Two consecutive reaction steps are observed: the first step is dependent on the incoming ligand concentration and the second step which is independent, is assigned to ring closure. The activation parameters, conductivity data and IR data obtained also support the proposed mechanism.     

Metal–Ligand Misfits: Facile Access to Rhenium–Oxo Corroles by Oxidative Metalation

With the exception of a single accidental synthesis, rhenium corroles are unknown, but of great interest as catalysts and potential radiopharmaceuticals. Oxidative metalation of meso‐triarylcorroles with [Re₂(CO)₁₀] in refluxing decalin has provided a facile and relatively high‐yielding route to rhenium(V)–oxo corroles. The complexes synthesized could all be fully characterized by single‐crystal X‐ray structure analyses.     

Invariant Solutions of Inhomogeneous Universe with Electromagnetic Field in Lyra Geometry

The present study deals with the cylindrically symmetric inhomogeneous cosmological models for perfect fluid distribution with electro-magnetic field in Lyra geometry. Lie group analysis has been used to identify the generators (symmetries) that leave the given system of partial differential equations (field equations) invariant. With the help of canonical variables associated with these generators, the assigned system of partial differential equations is reduced to an ordinary differential equations whose simple solutions provide nontrivial solutions of the original system. They obtained a new class of invariant (similarity) solutions by considering the potentials of metric and displacement field are functions of coordinates t and x. The physical behavior of the derived models are also discussed.     

Oxidative Metalation as a Route to Size‐Mismatched Macrocyclic Complexes: Osmium Corroles

Heavy‐element corroles are of great interest as optical sensors, near‐IR dyes, phosphors, organic light‐emitting diodes, and anticancer compounds. Insertion of 5d metals into corroles, however, is often a difficult and unpredictable process. Against this backdrop, oxidative metalation of meso triarylcorroles with [Os₃(CO)₁₂]/NaN₃ in refluxing 1:2 diethylene glycol monomethyl ether/glycol has provided a convenient and relatively high‐yielding route to nitridoosmium(VI) corroles, three of which could be characterized with single‐crystal X‐ray structure analysis.     

If Gauss–Bonnet interaction plays the role of dark energy

A cosmological model has been constructed with Gauss–Bonnet-scalar interaction, where the Universe starts with exponential expansion but encounters infinite deceleration, q→∞$q\to \infty$ and infinite equation of state parameter, w→∞$w\to \infty$. During evolution it subsequently passes through the stiff fluid era, q=2$q=2$, w=1$w=1$, the radiation dominated era, q=1$q=1$, w=1/3$w=1/3$ and the matter dominated era, q=1/2$q=1/2$, w=0$w=0$. Finally, deceleration halts, q=0$q=0$, w=−1/3$w=-1/3$, and it then encounters a transition to the accelerating phase. Asymptotically the Universe reaches yet another inflationary phase q→−1$q\to -1$, w→−1$w\to -1$. Such evolution is independent of the form of the potential and the sign of the kinetic energy term, i.e., even a non-canonical kinetic energy is unable to phantomize (w<−1)$(w<-1)$ the model.     

DFT calculations on the spin-crossover complex Fe(salen)(NO): a quest for the best functional

DFT calculations on the spin-crossover complex Fe(salen)(NO) provide a striking illustration of the comparative performance of different exchange-correlation functionals vis-à-vis the issue of transition metal spin state energetics. Thus, although the "classic" pure functionals PW91 and BLYP favor the S = 1/2 state by about 10 kcal/mol, relative to the S = 3/2 state, the hybrid functional B3LYP favors the latter state by nearly the same margin. In contrast, the newer pure functionals OLYP and OPBE, based on the OPTX exchange functional, as well as the B3LYP* hybrid functional (which has 15% Hartree-Fock exchange, compared with 20% for B3LYP) predict nearly isoenergetic S = 1/2 and 3/2 states, as required for a spin-crossover complex. Intriguingly, the OLYP and B3LYP* spin density profiles for the S = 1/2 state of Fe(salen)(NO) are substantially dissimilar.     

Discrepancy between subcritical and fast rupture roughness: a cumulant analysis

Rough crack fronts in a sheet of paper, obtained during a creep experiment, do not follow true scaling laws. Local roughness exponents are estimated using the first order cumulant, a quantity recently introduced in the turbulence literature [J. Delour, J. F. Muzy, and A. Arneodo, Eur. Phys. J. B 23, 243 (2001)10.1007/s100510170074]. Using a large data set (102 fronts), we find a significant difference in local roughness between the slow (subcritical) and the fast growth regime.