Two-dimensional dye crystals with controllable optical properties

Abstract

The structure, molecular ordering and optical properties of single crystals of cyanine dyes grown by adsorption from a water subphase to a positively charged lipid monolayer are discussed. These crystals are one monolayer thick, of uniform dimensions between 10 and 100μm (depending on nucleation conditions) and of rectangular shape. Single crystals were studied by transmission electron diffraction and by polarized absorption and emission spectroscopy. We show that the crystals consist of two rows of densely stacked molecules with two different orientations of the long molecular axes. This leads to two perpendicularly polarized absorption bands. The measured splitting is in accordance with results of extended dipole calculations. The latter were performed for crystals of three slightly different molecules where the angles between the long axes varied between 70° and 100°. The aliphatic tails form a lattice which is epitaxially related to the centered rectangular one of the dyes. It is incommensurate, and the tails are tilted with tilt azimuth either parallel to the a or to the b axis (depending on the type of dye) of the dye lattice. The procedure allows formation of mixed crystals with structural parameters, depending on composition, between those of the pure compounds. Hence also the optical spectra can be tuned via composition maintaining sharp band edges and emission bands.