Felix Scheliga

How chromophore shape determines the spectroscopy of phenylene-vinylenes: origin of spectral broadening in the absence of aggregation.

Single oligo(phenylene-vinylene) molecules constitute model systems of chromophores in disordered conjugated polymers and can elucidate how the actual conformation of an individual chromophore, rather than that of an overall polymer chain, controls its photophysics. Single oligomers and polymer chains display the same range of spectral properties. Even heptamers support pi-electron conjugation across approximately 80 degrees curvature, as revealed by the polarization anisotropy in excitation and supported by quantum chemical calculations. As the chain becomes more deformed, the spectral linewidth at low temperatures, often interpreted as a sign of aggregation, increases up to 30-fold due to a reduction in photophysical stability of the molecule and an increase in random spectral fluctuations. The conclusions aid the interpretation of results from single-chain Stark spectroscopy in which large static dipoles were only observed in the case of narrow transition lines. These narrow transitions originate from extended chromophores in which the dipoles induced by backbone substituents do not cancel out. Chromophores in conjugated polymers are often thought of as individual linear transition dipoles, the sum of which make up the polymers optical properties. Our results demonstrate that, at least for phenylene-vinylenes, it is the actual shape of the individual chromophore rather than the overall chromophoric arrangement and form of the polymer chain that dominates the spectroscopic properties.

Unsaturated copolyesters of lactide

Four classes of unsaturated copolyesters of L-lactide were prepared either from isosorbide or bis(hydroxymethyl)tricyclodecane in combination with fumaric acid or from 1,4-butenediol or 1,4-butynediol with terephthalic acid. All syntheses were performed in such a way that lactide was oligomerized with a diol as the initiator and the resulting oligomers were polycondensed with a dicarboxylic acid dichloride either in a one-pot synthesis or in a two-step procedure. For most copolyesters the SEC measurements gave weight average molecular weights in the range of 30–60 kg mol−1 and dispersities in the range of 4.2–6.2. The MALDI-TOF mass spectra displayed a high content of cycles and indicated an irreversible kinetic course of all polycondensations. Glass-transition temperatures (Tg) above 90 °C were only found for two copolyesters of isosorbide. Addition of bromine to copolyesters of 1,4-butenediol yielded flame retarding biodegradable polymers.

Optoelectronic and photonic properties of liquid crystals: electroluminescence and photorefractivity

Beyond conventional electrooptic applications, liquid crystals become increasingly important in the topical field of organic electronics. Here, some fundamental findings are reviewed and two examples for the combination of liquid crystals and organic semiconductors are described in more detail. The first part of the paper describes the electroluminescent properties of very thin layers of aligned p-(phenylene vinylene) oligomers, which are embedded in a stack of thin organic semiconductor layers and sandwiched between two electrodes. Both the wavelength of the emitted luminescence (varying from green to red) and the dichroic ratio increase with increasing length of the aromatic backbone of the molecules. High brightness and low threshold voltages could be achieved. The photorefractive system described in the second part of the paper consists of small droplets of a low molar mass liquid crystal, which are dispersed in a photoconducting polymer. Two-beam coupling experiments indicate a high performance at reasonable external voltages. From dynamic diffraction measurements, the amplitude of the internal space charge field can be estimated.