Conformational equilibria and photoinduced tautomerization in 2-(2′-pyridyl)pyrrole

Depending on the polarity and protic abilities of the solvent, 2-(2′-pyridyl)pyrrole can exist in either syn or anti rotameric forms. In nonpolar solvents, intramolecular excited state single proton transfer is observed, manifested by the appearance of low-energy tautomeric emission. The solvent-assisted excited state double proton transfer reaction is also detected. DFT calculations confirm low barriers for both single and double proton transfer processes in the lowest excited singlet state and show different character of the tautomerization in both cases: in the intramolecular reaction, mutual approach of two nitrogen atoms plays an important role.     

1,4-dioxane as a solvent in spectroscopy and photochemistry

Commercially available 1,4-dioxane, even of spectroscopic grade, contains various impurities that arise mostly from reaction of the solvent with oxygen. Aspects relevant to the spectroscopy and photochemistry of the dioxane/oxygen system are discussed. Methods of purification and storage of the solvent are presented.     

Exchange interactions in copper(II) complexes with tridentate Schiff bases: EPR and magnetic studies

The influence of the nature of ligands upon the magnetic and EPR properties was investigated for the series of polynuclear Cu(II) complexes with tridentate Schiff bases. A similar tendency of changes in the |J| and D parameters was found for binuclear Cu(II) complexes with ligands derived from condensation of 3-amino-1-propanol with 2-hydroxyaldehydes and acetylacetone as well as for Cu(II) complexes with condensation products of o-aminophenol and β-diketones. The Cu(II) complex with Schiff base of 1-amino-2-propanol and acetylacetone exhibits ferromagnetic behaviour suggesting tetrameric structure.     

On a new variational principle in general relativity and the energy of the gravitational field

A new variational principle based on the affine connection in space-time is proposed. This leads to a new formulation of general relativity. The gravitational field is a field of inertial frames in space-time. The metricg appears as a momentum canonically conjugate to the gravitational field. In the case of simple matter fields, e.g., scalar fields, electromagnetic fields, Proca fields, or hydrodynamical matter, the new formulation is equivalent to the traditional one. A new formulation of conservation laws is proposed.     

The structure,magnetic and spectral properties of 4-acetylpyridine N-oxide complexes of copper(II) propionates

The synthesis and characterization of CuX₂L; (X = CH₃CH₂COO^?, ClCH₂CH₂COO^?, CH₃CHClCOO^? or CH₃CCl₂COO^?; and L = 4-acetylpyridine N-oxide) is reported. The characterization of these compounds was based on electronic, infrared and EPR spectra, as well as magnetic measurements over the temperature range. Several correlations between the spectral and magnetic data as well as pK_a values of the respective acids were found and discussed. On the basis of spectral and magnetic data the structures of the compounds are discussed.     

Phosphonates containing sulfur and selenium. Synthesis of vinylphosphonates bearing α-sulfenyl, α-selenenyl, α-sulfinyl and α-seleninyl moieties and studies on nucleophilic addition

The selenenylation of racemic and optically active α-phosphoryl sulfoxides is a key step leading efficiently to α-phosphorylvinyl sulfoxides or α-phosphorylvinyl selenides depending on the reaction conditions. Oxidation of α-phosphorylvinyl selenides and subsequent thermolysis of selenoxides afford alkynylphosphonates. Studies of the stereochemical course of nucleophilic addition to α-phosphoryl sulfoxides show high facial stereoselectivity of the reaction, however, epimerisation at the α-carbon atom leads to mixtures of diastereomers.     

Ultrafast fragmentation and ionisation dynamics of ammonia clusters

The formation of protonated and unprotonated ammonia cluster ions is studied by femtosecond two colour two photon pump-probe techniques applied to (NH₃) _n and (ND₃) _n clusters withn up to 8. The fourth harmonic (～ 200 nm, 6.2 eV, 160 fs) of a Ti: Sapphire laser pulse is used to excite the clusters in a state corresponding to theà state of NH₃ while the third harmonic (267 nm, 4.65 eV) is used for the subsequent ionisation step. Employing a combination of the optical Bloch equations for the excitation process and rate equations for the cluster dynamics we calibrate the zero time delay and carefully analyse the time dependence of the pump-probe signal. Several distinct intermediate steps in the time evolution can be distinguished, having characteristic time constants ranging from 40 fs to over 100 ps. They are discussed in a consistent scheme for the excitation, ionisation and protonation dynamics, accounting also for characteristic differences observed between deuterated and undeuterated species. A particularly remarkable time dependence of the homogeneous (NH₃) ₂ ⁺ cluster ion signal is interpreted as a fingerprint of internally protonated neutral precursors of the type NH₃NH₂NH₄.