Efficient synthesis of methyl 4-chloro-6-fluoro-3-formyl-2H-chromene-2-carboxylate and its derivatives

Abstract  

Methyl 4-chloro-6-fluoro-3-formyl-2H-chromene-2-carboxylate was synthesized conveniently using Vilsmeier reagent. A series of new 2H-chromenes was prepared in high yields by introducing a corresponding β-halovinylaldehyde into condensation and cyclization reactions with active methylene compounds.     

Kinetics and Optical Properties of the Strongly Driven Gas Medium of Interacting Atoms

This paper investigates stimulated emission and absorption near resonance for a driven system of interacting two-level atoms. Microscopic kinetic equations for the density matrix elements of N-atom states including atomic motion are built, taking into account atom-field and atom-atom interactions. Analytical solutions are given for the resulting macroscopic equations in different limits, for a system composed of a strong coherent “pump” field and a weak counter-propagating “probe” field. It was shown that the existence of a dipole-dipole (long-range) interaction between atoms separated by distance less than the pump wave-length can cause the formation of periodic polarization and population structures (gratings in time and space) in the pumped medium without a probe field. The magnitude of pump induced population grating can have a strong dependence on the relation between the pump field detuning and the polarization decay rate. The “interaction” between pump and probe induced polarization/population gratings through a dipole-dipole interaction mechanism causes the absorption line shape asymmetry. Under certain conditions, this asymmetry is revealed in increasing probe gain for the “red”-shifted (relative to pump) probe and suppressing the gain for the “blue”-shifted probe field when pump is “red”-shifted relative to the ensemble averaged resonant frequency. The theoretical results are consistent with experimental data for the probe gain or absorption as the function of frequency and the dependance of the gain on atomic density for sodium vapor when the pump laser is tuned near the D ₂ line. Here the dependance of gain on particle density was explained in the terms of the long-range interaction between the atoms.     

Self-assembly of a hexagonal boron nitride nanomesh on Ru(0001)

Hexagonal boron nitride (h-BN) nanostructures were grown on Ru(0001), and are very similar to those previously reported on Rh(111). They show a highly regular 12 x 12 superstructure, comprising 2 nm wide apertures with a depth of about 0.1 nm. Valence band photoemission reveals two distinctly bonded h-BN species, and X-ray photoelectron spectroscopy indicates an h-BN monolayer film. The functionality of the h-BN/Ru(0001) nanomesh is demonstrated by using this structure for the assembly of gold nanoclusters.     

Gaps in the spectrum of the Neumann Laplacian generated by a system of periodically distributed traps

The article deals with a convergence of the spectrum of the Neumann Laplacian in a periodic unbounded domain Ω^ϵ depending on a small parameter ϵ > 0. The domain has the form , where S^ϵ is an -periodic family of trap-like screens. We prove that, for an arbitrarily large L, the spectrum has precisely one gap in [0,L] when ϵ is small enough; moreover, when ϵ → 0, this gap converges to some interval whose edges can be controlled by a suitable choice of geometry of the screens. An application to the theory of 2D photonic crystals is discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Merocyanines based on 1,3‐indanedione: electronic structure and solvatochromism

A series of merocyanines derived from 1,3‐indanedione and heterocycles of various electron‐donating properties was studied in detail. Their solvatochromic properties were explored in a wide range of solvent polarities to reveal the dependences of their chromacity and electronic structure on the key structural parameters – the properties of a donor heterocycle and the polymethine chain length. Also the dyes were studied by NMR spectroscopy and by quantum chemical calculations, both with the semiempirical AM1 and the non‐empirical density functional theory/B3LYP method. The solvatochromic properties of the explored dyes are rather close to those of merocyanines derived from malononitrile as acceptor group. Appreciable distinctions were observed only in protic ethanol; obviously, they are connected with the formation of solvent–solute H‐bonds in the case of 1,3‐indanedione derivatives. The electron‐acceptor properties of 1,3‐indanedione were found to be somewhat stronger in comparison with those of malononitrile even in aprotic solvents, contrary to the known literature data. Analysis of the merocyanines' molecular orbitals and simulation of their electronic spectra were carried out both in vacuum and in the solvent matrix, and the absorption electronic transitions were analyzed. Static nonlinear optical properties were calculated for both the new merocyanines and the corresponding cationic and anionic cyanine dyes. Copyright © 2010 John Wiley & Sons, Ltd.