Phase-matched four-wave mixing of isolated waveguide modes of high-intensity femtosecond pulses in a hollow photonic-crystal fiber

Hollow-core photonic-crystal fibers with a special dispersion profile are shown to allow phase-matched nonlinear optical interactions of isolated air-guided modes of high-intensity femtosecond laser pulses confined in the hollow fiber core. We present theoretical and experimental studies of the four-wave mixing of fundamental and second-harmonic pulses of a Cr:forsterite laser with an initial pulse duration of about 50 fs and an intensity on the order of 10¹⁴ W/cm² in waveguide modes of a hollow photonic-crystal fiber with a core diameter of about 13μm.     

Application of Horner–Emmons Olefination to the Crown-Ether Derivatives

An effective synthetic approach to the preparation of a new crown-ether vinylogs involving the Horner–Emmons olefination of carbonyl precursors with the use of C₂- and C₅-phosphonates was proposed. The effects of the conjugation chain length and the nature of the terminal polar functions in the phosphonate reagent on the yield and process stereoselectivity were discussed.     

Intermediates in the photochemical reaction for the formation of 2,7-dimethylacridine from ditolylamine and bromoform

The reaction of the photochemical synthesis of 2,7-dimethylacridine from di(para-tolyl)amine and bromoform was studied utilizing the method of microsecond impulse photolysis. The proposed new scheme for the formation of acridine assumes the recombination of the primary alkyl radicals at the nitrogen atom of the cation radical and/or the radical of the amine as the main route of the reaction. The data obtained indicate the common character of the nature of some intermediate stages and the structures of the intermediates in the photochemical formation of acridine compounds and triphenylmethane dyes from aromatic amines and halogenomethanes.Institute of Chemical Physics, Chernogolovka, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2044–2052, September, 1992.     

Study of the thermal stages of the photoinitiated cyclization of diarylamines with polyhalogenated methanes

On the basis of a study of the kinetics of the dark stages of the photoinitiated formation of acridines from substituted diphenylamines and bromoform the ionic nature of these stages was confirmed. Quantum chemical calculations confirmed the assumption of the dependence of the efficiency of cyclization on the charge state of the reacting molecules.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 564–569, March, 1991.     

Synthesis,complexation, and photochemistry of benzobisthiazole-based bis(crown ether)

Benzobisthiazole-based bis(crown ether) was synthesized and its complexation with alkali and alkaline earth cations was studied. Photochemical transformations of the free ligand and its complexes with alkaline earth cations involve E,Z-photoisomerization and [2+2] photocycloaddition. Dedicated to Academician N. S. Zefirov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2056–2065, September, 2005.     

Phosphorescence lifetime of naphthalene and phenanthrene in aggregated aromatic molecule-β-cyclodextrin-precipitant complexes

Aggregated aromatic molecule--cyclodextrin-precipitant complexes exhibit long-lived phosphorescence at room temperature in water after the chemical binding of oxygen. The temperature dependences of the phosphorescence lifetimes of naphthalene-h₈, naphthalene-de, and phenanthrene in the aggregates were measured. For example, the phosphorescence lifetimes of naphthalene-d₈ aggregated with -cyclodextrin and cyclohexane are equal to 25.1, 17.6, and 6.8 s at 77, 276, and 347 K, respectively, and that of phenanthrene aggregated with isooctane and -cyclodextrin are 3.24, 3.06, and 1.26 s at 268, 274, and 335 K, respectively. The temperature dependences of the phosphorescence lifetimes at room temperature are determined by the rate constants of the radiative and nonradiative transitions from the triplet state of an aromatic molecule.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2225–2228, September, 1996.     

Picosecond spectroscopy of trans-thioindigo

Transient species which are involved in direct photoisomerization of trans-thioindigo have been investigated using picosecond spectroscopy. The long-lived transient absorption band at 600 nm observed in previous nanosecond experiments was shown to be formed on a picosecond time scale. Such ultrafast formation is inconsistent with the accepted assignment of this band as triplet-triplet absorption.     

Crown-containing styryl dyes

Styryl dyes containing a crown ether group and a heteroaromatic moiety with a sulfoalkylN-substituent (1a,b) undergo photocyclodimerization in acetonitrile in the presence of Mg(ClO₄)₂ to give only the typeA isomer of cyclobutane derivative (2a,b). The photochemical regio- and stereoselectivity of the cycloaddition is explained by self-organization of thetrans-isomers of the styryl dyes upon complexation with the Mg²⁺ cations into dimers with a fixed mutual arrangement of multiple bonds.For part 7, see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1449–1452, August, 1993.     

Picosecond spectroscopy of phenylnaphthylethylenes

S_n←S₁ transitions in the trans isomers of 1-phenyl-2-(1-naphthyl)ethylene (Ph-1N) and 1-phenyl-2-(2-naphthyl)ethylene (Ph-2N) peaked at 510 nm are assigned by picosecond absorption spectroscope. The S₁ state lifetimes of both conformers of Ph-2N are shown to depend upon solvent viscosity, demonstrating the singlet mechanism of trans—cis photoisomerization and the stilbene-like behavior of Ph-2N.