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

The highly efficient, light-harvesting antennae systems present in chloro somes 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. High-resolution scanning tunneling microscopy and atomic force microscopy studies reveal the formation of two types of well-ordered ac-stacked aggregates on highly ordered pyrolytic graphite.