Self-assembled single- and double-stack pi-aggregates of chlorophyll derivatives on highly ordered pyrolytic graphite.

The highly efficient, light-harvesting antennae systems present in chlorosomes of green phototrophic bacteria, such as Chloroflexus aurantiacus, serve as a model for the design of bioinspired nanostructured materials. A semisynthetic zinc chlorin, derived from natural chlorophyll a, is used as a building block that self-assembles into excitonically coupled chromophore stacks. Temperature-dependent UV/Vis and circular dichroism spectroscopic measurements show the reversible formation of soluble chiral aggregates of this new zinc chlorin dye.

Efficient energy transfer from peripheral chromophores to the self-assembled zinc chlorin rod antenna: a bioinspired light-harvesting system to bridge the "green gap".

An artificial light-harvesting rod aggregate based on zinc chlorin and covalently linked naphthalene bisimide chromophore has been realized by self-assembly. Efficient energy transfer (phiET >/= 0.99) takes place upon excitation at 620 nm from peripheral naphthalene bisimides to the zinc chlorin rod aggregate backbone.

Gelation of a highly fluorescent urea-functionalized perylene bisimide dye.

[structure: see text] A urea-containing tetraphenoxy-substituted perylene bisimide has been synthesized, and its gelation ability has been studied. This functional dye forms fluorescent organogels in toluene and tetrachloromethane through self-assembly by hydrogen-bonding and pi-pi-stacking interactions. AFM and confocal laser scanning microscopy reveal the formation of fiberlike aggregates.

Supramolecular polymerization and gel formation of bis(merocyanine) dyes driven by dipolar aggregation.

Two highly dipolar merocyanine dyes were tethered by a rigid tris(n-dodecyloxy)xylylene unit that preorganizes the dyes for a supramolecular polymerization process through intermolecular aggregation of the dyes. UV/vis spectroscopy revealed a solvent dependent equilibrium between monomeric dyes and two different types of dye aggregates that are characterized by hypsochromically shifted D- and H-type absorption bands. Taking into account the ditopic nature of the supramolecular building blocks, the occurrence of the D-band indicates the formation of an oligomeric/polymeric supramolecular chain whereas the observation of the H-band suggests a higher order assembly.