The cover picture shows mesoscopic strands of highly fluorenscent perylene bisimide ± melamine assemblies as visualized by confocal fluorenscence microscopy. This technique does not only provide topological information such as related AFM or STM images, but truly shows the functionality of fluorescent optical networks of the present supramolecular system. The synthesis and structural investigations of the fluorescent mesoscopic superstructures is presented by F. Würthner et al. on p. 3871 ff. The author wishes to thank the BASF AG for kindly covering the costs for the cover picture
The combination of an atomic force microscope (AFM) with a Confocal Raman Microscope (CRM) has been used to study the composition of various thin films of polymer blends. The high spatial resolution of the AFM enables the morphological characterization of the polymer blends on the nanometer scale. Furthermore, when operating the AFM in Digital Pulsed Force Mode (DPFM), topographic information and local stiffness can be simultaneously recorded. This allows the material‐sensitive characterization of heterogeneous materials. Thin films where PMMA (at room temperature a glassy polymer) is blended with two different styrene‐butadiene rubbers are investigated. The presence of PMMA in both phase‐separated thin films allows the comparison of the mechanical properties of the two different rubber phases using DPFM‐AFM. When PMMA is blended with PET due to their similar mechanical properties (both are in the glassy state at room temperature) the assignment of the two phases to the corresponding polymers by AFM is rather difficult. Here, Raman spectroscopy provides additional information on the chemical composition of materials. In combination with a confocal microscope, the spatial distribution of the various phases can be determined with a resolution down to 200 nm. Therefore, the topographically different structures observed in AFM images can be associated to the chemical composition by using the Confocal Raman Microscope (CRM).
A series of three perylene tetracarboxylic acid bisimide dyes 3a-c bearing phenoxy substituents at the four bay positions of the perylene core were synthesized and their complexation behavior to complementary ditopic dialkyl melamines 8a-c was investigated. Binding constants and Gibbs binding energies for the hydrogen bonds between the imide and the complementary melamine moiety have been determined in several solvents by NMR and UV/Vis titration experiments with monotopic model compounds 5 and 9. The effects of the solvent polarity and specific solvent-solute interactions on the degree of polymerization of (3 x 8)n are discussed, and a general formula to estimate the chain length of [AA-BB]n nylon-type supramolecular polymers is derived. In addition to the formation of a hydrogen-bonded supramolecular chain. pi-pi interactions were observed for perylene bisimide-melamine assemblies 3b x 8b and 3b x 8c in aliphatic solvents. The orthogonal nature of hydrogen bonding and pi-pi interactions leads to three-dimensional growth yielding large-sized aggregates already in dilute solution. On suitable substrates, densely intertwined networks of nano- to mesoscopic strands are formed which have been investigated by electron microscopy, confocal fluorescence microscopy and optical polarization microscopy. The high fluorescence and excellent photostability of these superstructures is promising for future studies on energy migration and artificial light harvesting at the nano- and mesoscopic length scale.
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