Low band-gap oligomers and polymers

The relationship between electronic structure and chemical stability is discussed for three different classes of low band-gap oligomers and polymers. In oligo- and poly[n]acenes as well as in poly-(arylenemethide)s, the low band-gap character is connected with a high chemical reactivity due to an energetically favored rearomatization of olefinic or quinonoid substructures, respectively. For double-stranded oligo- and poly(rylene)s, the stability is dramatically increased. Therefore, rylenes appear especially promising in the field of low band-gap materials.     

Investigation of GaN heteroepitaxial layers by means of the kossel effect technique

GaN heteroepitaxial layers grown on spinel substrates have been investigated by the Kossel effect technique. The excitation of GaK_α X-rays inside the crystal lattice was carried out either by means of 1.25 MeV protons or 40 KeV electrons. Both methods give similar results concerning the values of the lattice parameters and the sign of polarity. Following the proton irradiation a lattice expansion normal to the surface occurs. A comparison of our results with those of other authors shows that the growth direction is the same for {111} spinel and {0001} sapphire substrates.     

The hydrogen bond in the solid state

The hydrogen bond is the most important of all directional intermolecular interactions. It is operative in determining molecular conformation, molecular aggregation, and the function of a vast number of chemical systems ranging from inorganic to biological. Research into hydrogen bonds experienced a stagnant period in the 1980s, but re-opened around 1990, and has been in rapid development since then. In terms of modern concepts, the hydrogen bond is understood as a very broad phenomenon, and it is accepted that there are open borders to other effects. There are dozens of different types of X-H.A hydrogen bonds that occur commonly in the condensed phases, and in addition there are innumerable less common ones. Dissociation energies span more than two orders of magnitude (about 0.2-40 kcal mol(-1)). Within this range, the nature of the interaction is not constant, but its electrostatic, covalent, and dispersion contributions vary in their relative weights. The hydrogen bond has broad transition regions that merge continuously with the covalent bond, the van der Waals interaction, the ionic interaction, and also the cation-pi interaction. All hydrogen bonds can be considered as incipient proton transfer reactions, and for strong hydrogen bonds, this reaction can be in a very advanced state. In this review, a coherent survey is given on all these matters.     

Persistence of nematic liquid crystalline phase in a polyfluorene‐based organic semiconductor: A high pressure study

The role of high pressure on a low molecular weight nematic liquid crystalline organic semiconductor, ethyl‐hexyl substituted polyfluorene (PF2/6) is investigated using photoluminescence (PL), Raman scattering, and X‐ray scattering studies at pressures from 1 to 8 GPa. The PL and the Raman data under pressure are consistent with each other with no abrupt changes in the pressure coefficients of PL or Raman peaks. The PL energies redshift and broaden, consistent with both enhanced intra‐ and interchain interactions. The Raman peak positions yield pressure coefficients similar to other phenyl based π‐conjugated polymers. The broadening of a doublet peak in the 1135 cm^?1 region indicates a more planar backbone conformation with increasing pressure. X‐ray scattering indicates that the torsion angle between adjacent repeats reduces with increasing pressure and reverts back with decompression. The intermolecular structure is weakly ordered (frozen nematic) and essentially maintained with increasing pressure, in contrast to a high molecular weight PF2/6. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1014–1023     

Absorption and subsequent emission saturation of two-photon excited materials: theory and experiment

The saturation of two-photon absorption and the subsequent photoluminescence of matter under ultrafast laser pulse excitation are studied. For this purpose the experimental results of using two organic conjugated polymers as model substances are discussed theoretically. One model is based on the commonly used hyperbolic approach, whereas the new theory introduced correctly describes the saturation in two-photon spectroscopy and fits the experiment closely. The new model permits microscopic analysis of the absorption saturation process and makes possible an estimate of the two-photon absorption coefficient from the saturation intensity.     

Gravitational redshift experiments with the high-resolution Mössbauer resonance in67Zn

A gravitational tedshift (GRS) experiment using the high-resolution Mössbauer resonance in⁶⁷Zn is described. The tiny Doppler motion of the source can be checked by a dc-SQUID based displacement sensor. The results on the GRS strongly indicate that solid-state effects, which are difficult to control experimentally, finally limit the accuracy that Mössbauer measurements can provide in determining the GRS. We argue that for this reason conventional Mössbauer experiments most probably will not be able to compete with other methods in future GRS measurements of very high precision.     

Bulk and microscopic properties of copolymer networks in mixed aqueous solvents

Amphiphilic films and hydrogels have been prepared from ethanol/water solutions containing a hydrocarbon-grafted water-soluble cellulose ether. These materials are characterized by dispersed hydrophobic microdomains which form spontaneously in the solvent due to the inherent incompatibility of the side chains with water. At low applied shear stress, the microdomains behave as temporary linkages of finite lifetimes, imparting viscoelastic properties to the networks. The molecular weight between microdomains was found to be independent of the volume fraction of polymer in the gel, and the number of linkages per backbone ranges from 22.8 ± 1.3 to 26.2 ± 1.5 over the frequency range 30–50 rad/s. The behavior of the solutions and gels was characterized using fluorescence and dynamic rheological measurements. It was demonstrated that the microdomains are capable of sequestering water-insoluble solutes. © 1992 John Wiley & Sons, Inc.