Spin-state dynamics of a photochromic iron(II) complex and its immobilization on oxide surfaces via phenol anchors

This work presents a detailed study of the photo-induced spin-state dynamics of the photochromic iron(II) complex 1, where the metal ion is in the field of a tripodal hexa-imine ligand with protolysable phenol groups. The nature of the complex’s ground state has been identified as a spin singlet by ¹H NMR and steady-state UV/vis spectroscopies, and its distorted octahedral structure was analyzed via crystal structure determination. Sub-picosecond and nanosecond time-resolved laser flash photolysis experiments identify the long-lived quintet state of 1 as the selective product of photoexcitation in the UV/vis spectral region. Thermal barriers of spin-state interconversion as a function of solvent and added base are derived from temperature-dependent rates of transient decay. Ground-state recovery is found to be significantly affected by the solvent and is strongly enhanced, in particular, by base-driven solvolysis of the ligand’s phenol groups. Partial spontaneous deprotonation of the phenolic hydroxyl groups of 1 seems to prevail on metal oxide surfaces, i.e. on alumina. Composite materials, like 1 at Al₂O₃, that retain the characteristic spectral features of the parent iron(II) complex can be readily obtained by wet impregnation of hydrous alumina with solutions of 1.     

Wall-shear-stress and near-wall turbulence measurements up to single pixel resolution by means of long-distance micro-PIV

A digital large-format long-distance micro-particle image velocimetry system (μ-PIV) was developed to measure the wall-shear-stress and the near-wall flow properties in a laminar, transitional and turbulent boundary layer flow along a flat plate, non-intrusively with high accuracy and spatial resolution. To achieve the desired measurement accuracy and spatial resolution, all experimental limitations associated with the seeding, light-sheet, out-of-focus particles, optical aberrations and distortions were successfully solved and various spatial correlation image analysis approaches based on the two-point or single-pixel ensemble correlation were developed, analyzed and compared with the state-of-the-art spatial correlation techniques. The instrument is well suited to prove fundamental fluid mechanical hypotheses such as the universality of the constants κ and B of the logarithmic law. However, for the analysis of flows at large Reynolds and Mach numbers, where small spatial dimensions and strong flow gradients prevent accurate measurements, this technique can be applied as well.     

Resonant Raman spectra of diindenoperylene thin films

Resonant and preresonant Raman spectra obtained on diindenoperylene (DIP) thin films are interpreted with calculations of the deformation of a relaxed excited molecule with density functional theory (DFT). The comparison of excited state geometries based on time-dependent DFT or on a constrained DFT scheme with observed absorption spectra of dissolved DIP reveals that the deformation pattern deduced from constrained DFT is more reliable. Most observed Raman peaks can be assigned to calculated A(g)-symmetric breathing modes of DIP or their combinations. As the position of one of the laser lines used falls into a highly structured absorption band, we have carefully analyzed the Raman excitation profile arising from the frequency dependence of the dielectric tensor. This procedure gives Raman cross sections in good agreement with the observed relative intensities, both in the fully resonant and in the preresonant case.