Ring opening reactions of pyromellitic dianhydride for the synthesis of first row transition metal dicarboxylate complexes

The ring opening reaction of pyromellitic dianhydride by methanol is an effective method to prepare first row transition metal dicarboxylate complexes. The reactions of different first row transition metal salts with pyromellitic dianhydride in the presence of nitrogen donating bidentate ligands such as 1,10-phenanthroline and 2,2′-bipyridine gives different compositions depending on the ligand and the metal salts used. For example, the reaction of nickel(II) acetate with pyromellitic dianhydride in the presence of 1,10-phenanthroline results in the formation of a carboxylato bridged nickel(II) metallacycle through the ring opening reaction of pyromellitic dianhydride (PAH) at the 1 and 3-positions, whereas a mononuclear tetra-aqua 2,2′-bipyridine nickel(II) complex is formed in a similar reaction of nickel(II) acetate through ring opening at the 1,4-position of PAH. Mononuclear cobalt(II) dicarboxylate complexes are formed from the ring opening reaction of pyromellitic dianhydride in methanol in the presence of the nitrogen donor ligands 1,10-phenanthroline or 2,2′-bipyridine. Copper(II) chloride on reaction with PAH and 2,2′-bipyridine gives a mononuclear complex via ring opening at the 1 and 4-positions; having chlorides inside and outside the coordination sphere. Whereas, the reaction of copper(II)acetate gives dinuclear copper complexes having a monodentate carboxylato bridge arising from the carboxylato groups at the 1 and 4-positions on the aromatic ring. The crystal structures of all the complexes have been determined.     

Nonsolvent application of ionic liquids: organo-catalysis by 1-alkyl-3-methylimidazolium cation based room-temperature ionic liquids for chemoselective N-tert-butyloxycarbonylation of amines and the influence of the C-2 hydrogen on catalytic efficiency

1-Alkyl-3-methylimidazolium cation based ionic liquids efficiently catalyze N-tert-butyloxycarbonylation of amines with excellent chemoselectivity. The catalytic role of the ionic liquid is envisaged as "electrophilic activation" of di-tert-butyl dicarbonate (Boc(2)O) through bifurcated hydrogen bond formation with the C-2 hydrogen of the 1-alkyl-3-methylimidazolium cation and has been supported by a downfield shift of the imidazolium C-2 hydrogen of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][NTf(2)]) from δ 8.39 to 8.66 in the presence of Boc(2)O in the (1)H NMR and a drastic reduction of the catalytic efficiency with 1-butyl-2,3-dimethylimidazolium ionic liquids that are devoid of the C-2 hydrogen. The differential time required for reaction with aromatic and aliphatic amines has offered means for selective N-t-Boc formation during inter and intramolecular competitions. Preferential N-t-Boc formation with secondary aliphatic amine has been achieved in the presence of primary aliphatic amine. Comparison of the catalytic efficiency for N-t-Boc formation with a common substrate revealed that [bmim][NTf(2)] is superior to the reported Lewis acid catalysts.     

Quasiprobability distributions in open quantum systems: Spin-qubit systems

We study nonclassical features in a number of spin-qubit systems including single, two and three qubit states, as well as an N$N$ qubit Dicke model and a spin-1 system, of importance in the fields of quantum optics and information. This is done by analyzing the behavior of the well known Wigner, P$P$, and Q$Q$ quasiprobability distributions on them. We also discuss the not so well known F$F$ function and specify its relation to the Wigner function. Here we provide a comprehensive analysis of quasiprobability distributions for spin-qubit systems under general open system effects, including both pure dephasing as well as dissipation. This makes it relevant from the perspective of experimental implementation.     

On the characterization of non-stationary chaotic systems: Autonomous and non-autonomous cases

Properties of non-stationary dynamical systems are studied using the concept of a snapshot attractor which takes into account a large number of initial conditions within the basin of attraction. In this paper, both autonomous and non-autonomous systems are considered. We have discussed three different ways of inducing non-stationarity in a chaotic system—(a) when the parameter changes in a linear fashion, (b) when the parameter changes in a random fashion and (c) when it is governed by an equation inducing a chaotic change in it. Here all the variations are with respect to time. Though the first and second situations have already been considered in Romeiras et al. (1990) [1] and Serquina et al. (2008) [2], the last one has never been considered before. In each case the basic fractal properties and the famous Pesin identity are proved numerically. The Lyapunov exponents, which are calculated via an averaging procedure, lead to the expected values.     

Low temperature synthesis of zinc ferrite nanoparticles

Zinc ferrite (ZnFe₂O₄) nanocrystalline powder materials with various particle sizes were prepared by a unique solid-state combustion method. Phase purity of ZnFe₂O₄ was confirmed by X-ray diffraction studies. High resolution transmission electron microscopic analysis and selected area diffraction pattern also confirmed the correct crystalline phase formation. Particle size was determined from both the transmission electron microscopic images and also from the XRD peak broadening analysis. Oxidation states of different elements present in ZnFe₂O₄ were determined by X-ray photoelectron spectroscopy. Frequency dependent dielectric constant and a.c. conductivity were measured as a function of particle size and both of them were found to decrease with decreasing particle size. These studies indicated that good quality zinc ferrite nanocrystalline powdered materials can be synthesized at low temperature.     

Nonlinear Dynamics of a Flexible Spinning Disc Coupled to a Precompressed Spring

This paper analyses the nonlinear transverse vibrations of a rotating, clamped-free, flexible disc coupled to a precompressed spring. This is representative of a large class of loadings in rotating disc systems such as air jet and electromagnetic excitation commonly used in experiments. Such a loading induces a simultaneous critical speed resonance and parametric instability. The disc is modelled as a Von Kármán plate, and the equations of motion are discretised by a Galerkin projection onto a pair of 1:1 internally resonant modes. The large amplitude wave motions and their stabilities are studied using the averaging method and via numerical continuation techniques. The analysis is carried out in a co-rotating as well as a ground-fixed frame. Numerical simulations are used to verify the above analyses. The response predicted by these analyses is substantially different from that arising from a critical speed resonance or of a parametric instability alone. As many as five equilibrium solutions can coexist at supercritical speed. Two distinct regimes of large amplitude response appear to exist depending on the relationship between the strength of the parametric excitation and the damping. The existence of these regimes underscores the subtle competition between critical speed resonance and parametric instability that is likely to be observed in experiments near critical speed in such systems.Contributed by Prof. A.K. Bajaj.     

Enhancement of Non-Gaussianity and Nonclassicality of Photon-Added Displaced Fock State: A Quantitative Approach

Non-Gaussian and nonclassical states and processes are already found to be important resources for performing various tasks related to quantum gravity and quantum information processing. Considering these facts, a quantitative analysis of the nonclassical and non-Gaussian features is performed here for photon added displaced Fock state, as a test case, using a set of measures, namely entanglement potential, Wigner–Yanese skew information, Wigner logarithmic negativity, and relative entropy of non-Gaussianity. It is observed that Fock parameter always increases the amount of nonclassicality and non-Gaussianity, while photon addition is effective only for small values of the displacement parameter. Further, the nonclassical and non-Gaussian effects decrease initially with an increase in the displacement parameter before increasing for the large displacement to saturate to the corresponding Fock state (equivalently displaced Fock state) value. Finally, dynamics of the Wigner function under the effect of photon loss channel is used to show that only highly efficient detectors are able to detect Wigner negativity.     

Regiocontrolled Nitration of 4-Quinolones at Ambient Conditions

Regiocontrolled nitration of 4-quinolone, the highly privileged scaffold, has been developed at ambient conditions. The nitro group can selectively be introduced at diverse positions simply by tuning the reactivity of the moiety. Discrimination is being achieved through the selective functionalization of the free N-H group. The functional group has been screened theoretically with the help of Fukui function and local softness calculation. Theoretical predictions are synchronized well with the experimental findings. Finally, this nitration technique allows quick access to the structurally diverse 4-quinolones.