Structural Determination of a Photochemically Active Diplatinum Molecule by Time‐Resolved EXAFS Spectroscopy

Metallica : A large contraction of the Pt? Pt bond in the triplet excited state of the photoreactive [Pt₂(P₂O₅H₂)₄]^4? ion is determined by time‐resolved X‐ray absorption spectroscopy (see picture). The strengthening of the Pt? Pt interaction is accompanied by a weakening of the ligand coordination bonds, resulting in an elongation of the platinum–ligand bond that is determined for the first time.

     

Simulations of X-ray absorption spectra: the effect of the solvent

We perform quantum mechanics/molecular mechanics molecular dynamics simulations on the [Pt(2)(P(2)O(5)H(2))(4)](4-) (abbreviated PtPOP) complex; in water, dimethylformamide and ethanol. These are used to calculate the ground state X-ray absorption spectrum of the complex. The structural parameters from X-ray spectra are usually extracted using a fit of the experimental data. In such simulations the solvent is neglected meaning that any effect of the local environment will be compensated for by structural changes of the solute, leading to possible discrepancies in the extracted structural parameters. Our simulations show a significant solvent effect on the spectra, which has important implications for the structural analysis of molecules in solution.     

Ultrafast fluorescence studies of dye sensitized solar cells

Time-resolved fluorescence spectra from the RuN719 dye exhibit very short lifetimes (<30 fs) in solutions, on non-injecting substrates and on injecting ones. This reveals <10 fs intramolecular energy redistribution competing with the injection. We conclude that injection proceeds on a sub-10 fs time scale from non-thermalized levels of the dye.     

Ultrabroadband femtosecond two-dimensional ultraviolet transient absorption

We present a broadband two-dimensional transient absorption setup for the UV around 300 nm with a time resolution of 150 fs. A narrowband, frequency tunable pump pulse and a broadband probe pulse are generated from the output of a noncollinear optical parametric amplifier operated at 20 kHz repetition rate and combined in a spectrally resolved transient absorption experiment. The high repetition rate and low noise of the setup allow us to acquire high quality two-dimensional data as a function of time delay with an unsurpassed frequency window of 10,000 and 8000 cm(-1) along the probe and pump axis, respectively. The performance of the setup is demonstrated on 2,5-Diphenyloxazol dissolved in cyclohexane.     

Photexcitation of aqueous ruthenium(II)-tris-(2,2'-bipyridine) with high-intensity femtosecond laser pulses

We report a femtosecond pump-probe study on the photochemistry of concentrated aqueous solutions of [RuII(bpy)3]2+, as a function of pump power (up to 2 TW/cm2) at 400 nm excitation. The transient absorption spectra in the 345-660 nm range up to 1 ns time delay enable the observation of the following photoproducts: the triplet 3MLCT (metal-to-ligand-charge-transfer) excited state, the reduced form [RuII(bpy)3]+, the oxidized species [RuIII(bpy)3]3+, and the solvated electron e(aq). The 3MLCT state is formed within the excitation pulse and undergoes vibrational relaxation in 3-5 ps, as evidenced by the shift of the ligand-centered (LC) absorption band below 400 nm. Even at the highest pump powers, the majority of e(aq) originates from multiphoton ionization of [RuII(bpy)3]2+ and not from the solvent, generating [RuIII(bpy)3]3+ as a byproduct. At 10 ps time delay, the total concentration of the three product species is balanced by the depleted concentration of [RuII(bpy)3]2+, even at the highest fluences used, indicating that no further reaction products significantly contribute to the overall photochemistry. On the 100 ps time scale, most probably diffusion-controlled reduction of ground-state [RuII(bpy)3]2+ by solvated electrons occurs, next to recombination between e(aq) and [RuIII(bpy)3]3+.     

Convergence of Global and Bounded Solutions of a Second Order Gradient like System with Nonlinear Dissipation and Analytic Nonlinearity

In this paper we establish convergence to equilibrium of all global and bounded solutions of a gradient like system of second order with nonlinear dissipation and analytic nonlinearity. We estimate also the rate of convergence.     

Viscous Fingering Instability in Porous Media: Effect of Anisotropic Velocity-Dependent Dispersion Tensor

The viscous fingering of miscible flow displacements in a homogeneous porous media is examined to determine the effects of an anisotropic dispersion tensor on the development of the instability. In particular, the role of velocity-dependent transverse and longitudinal dispersions is investigated through linear stability analysis and nonlinear simulations. It is found that an isotropic velocity-dependent dispersion tensor does not affect substantially the development of the instability and effectively has the same effect as molecular diffusion. On the other hand, an anisotropic velocity-dependent dispersion tensor results in different instability characteristics and more intricate finger structures. It is shown that anisotropic dispersion has profound effects on the development of the fingers and on the mechanisms of interactions between neighboring fingers. The development of the new finger structures is explained by examining the velocity field and characterized qualitatively through a spectral analysis of the average concentration and an analysis of the variations of the sweep efficiency and relative contact area.     

Chemo- and Regioselective 1,3-Dipolar Cycloaddition of 2-Diazopropane over 1,4-Benzoquinone: Synthesis of New Pyrazoloquinones

Abstract

1,3-Dipolar cycloaddition reaction of 2-diazopropane 1 with 1,4-benzoquinone 2 carried out at ?20 °C led to a minor mono-cycloadduct 4 and mixture of bis-cycloadducts 6 and 7. The same addition realized with 3H-pyrazole 7 at ?60 °C for 2 h yields a mixture of compounds 8 and 9 and results in O-alkylation. The reaction of 3H-pyrazoles 4 and 7 with dimethylsulfoxide and oxalyl chloride under Swern conditions led to pyrazolenines 11 and 12.