Highly ordered silver nanowire arrays have been obtained by pulsed electrodeposition in self-ordered porous alumina templates. Homogeneous filling of all the pores of the alumina template is achieved. The interwire distance is about 110 nm corresponding to a density of silver nanowires of 61ϫ10 9 in. Ϫ2 and the diameter can be varied between 30 and 70 nm. The silver wires are monocrystalline with some twin lamella defects and grow perpendicular to the ͗110͘ direction. The previously encountered difficulty to obtain 100% filling of the alumina pores is discussed in the framework of electrostatic instabilities taking into account the different potential contributions during electrodeposition. To obtain homogeneously filled pore membranes, a highly conductive metal containing electrolyte, a homogeneous aluminum oxide barrier layer, and pulsed electrodeposition are a prerequisite.

A tale of two modes: An end‐on copper superoxo complex was identified in a combined experimental and theoretical study. Theory clearly discloses the presence of an end‐on complex (see picture, O red, Cu pink, N green) with a minute isotopic resonance Raman splitting below experimental resolution. The results cast doubts on the uncritical use of 16O,18O isotopic‐labeling Raman experiments to discriminate end‐on from side‐on bonding modes in M(O2) complexes.

At low temperatures, the mononuclear copper(I) complex of the tetradentate tripodal aliphatic amine Me(6)tren (Me(6)tren = tris(2-dimethylaminoethyl)amine) [Cu(I)(Me(6)tren)(RCN)](+) first reversibly binds dioxygen to form a 1:1 Cu-O(2) species which further reacts reversibly with a second [Cu(I)(Me(6)tren)(RCN)](+) ion to form the dinuclear 2:1 Cu(2)O(2) adduct. The reaction can be observed using low temperature stopped-flow techniques. The copper superoxo complex as well as the peroxo complex were characterized by resonance Raman spectroscopy. The spectral characteristics and full kinetic and thermodynamic results for the reaction of [Cu(I)(Me(6)tren)(RCN)](+) with dioxygen are reported.

IR and Raman (λex = 785 and 1064 nm) spectra of Fe(phen)2(NCS)2 were recorded at T = 298 and 100 K, and the observed vibrations were assigned by comparison with the results obtained by DFT/BP86 calculations. The latter resulted, in accordance with crystal data, in an equilibrium geometry with C 2 symmetry for the low-spin state. In the high-spin state, two closely lying extrema were found on the BP86 energy hypersurface:  a saddle point (C 2 symmetry, one imaginary vibrational frequency) and, ca. 9.6 kJ/mol lower in energy, a minimum with C 1 symmetry. The differences in the geometrical parameters of the low-spin and high-spin states are in good agreement with the changes observed experimentally by X-ray crystallography. The calculated wavenumbers of the (NCS) vibration differed from the experimentally determined ones by more than 50 cm-1. Since it could be shown that anharmonicity is not the only cause for this discrepancy, two pyridins at optimized distances were included to model the interaction in the crystalline state. We find a correct wavenumber shift of this solid-state model versus the isolated molecule, corroborating the prominent role of intermolecular interactions, which are considered to be responsible for the sharp transition from the low-spin to the high-spin state. The partition function was calculated for both spin states by considering all calculated vibrational wavenumbers. The vibration-related entropy change connected with the low- to high-spin transition is determined via well-known thermodynamic relations. For the title compound, we found ΔS vib ≈ 19.5 J/(mol K), or approximately 40% of the experimentally determined total entropy change of 49 J/(mol K).

NIR−FT-Raman spectra of 1,10-phenanthroline were recorded of crystalline material and three different solutions (CD3OD, CHCl3, and CS2) in the wavenumber range 100−1800 cm-1. FT-IR spectra of the solid material were obtained for the range 400−1800 cm-1. A complete assignment of the experimental vibrational spectra (IR and Raman) of 1,10-phenanthroline is given on the basis of calculated frequencies and Raman intensities obtained from the DFT(BP86) harmonic force field. A satisfactory agreement of the harmonic BP86 wavenumbers with the fundamental experimental ones is found. This good agreement is due to a systematic error compensation for BP86 harmonic force fields. Raman intensities were calculated within the double harmonic approximation with different basis sets in order to investigate whether moderately sized triple-ζ basis sets with comparatively few polarization functions can properly describe nonresonant Raman scattering. A satisfactory agreement with experimental data for all in-plane vibrations is already obtained with a standard valence triple-ζ basis plus polarization functions. However, for out-of-plane modes, we found a pronounced dependence of frequencies and intensities on the basis set size, which can be well understood by comparison with the results obtained with a larger basis set. The Sadlej basis set, which is recommended for the calculation of electrical properties, leads to deviations of up to 90 cm-1 for out-of-plane vibrations. Since 1,10-phenanthroline is hygroscopic and can hardly be obtained in water-free form, particular attention is paid to the influence of bound solvent molecules, like water and methanol, on the vibrational spectrum. Model systems with single solvent molecules attached to the isolated phenanthroline molecule were studied. It was found that the wavenumber shifts induced are generally small.