Crystallographic models of ribbons and ribbon-based J-aggregate nanotubes from the geometry of tube ends.

Self-assembly into tubular structures typically proceeds by helical winding of ribbon intermediates, however, only the central parts of the tubes, that retain no information on the ribbon geometry, have received attention so far. We propose the procedure of establishing the crystal structure of ribbons and ribbon-based tubes on the basis of crystallographic analysis of the tube-end geometry, where the terminal parts of the ribbons fold and form characteristic mono/bilayer polygonal shapes. The terminal parts of flattened J-aggregate nanotubes of trimethine cyanine dye were clearly resolved in electron microscopy and atomic force microscopy images, and the original parallelogram shape of ribbons was reconstructed and interpreted as a two-dimensional [1-10]/[010] facetted crystal with inclined molecular π-stacks parallel to the long ribbon side.

Crystallography and Molecular Arrangement of Polymorphic Monolayer J-Aggregates of a Cyanine Dye: Multiangle Polarized Light Fluorescence Optical Microscopy Study.

The molecular orientation in monolayer J-aggregates of 3,3-di(γ-sulfopropyl)-5,5-dichlorotiamonomethinecyanine dye has been precisely estimated using improved linear polarization measurements in the fluorescence microscope in which a multiangle set of polarization data is obtained using sample rotation. The estimated molecular orientation supplemented with the previously established crystallographic constraints based on the analysis of the well-developed two-dimensional J-aggregate shapes unambiguously indicate the staircase type of molecular arrangement for striplike J-aggregates with the staircases oriented along strips. The molecular transition dipoles are inclined at an angle of ∼25° to the strip direction, whereas the characteristic strip vertex angle ∼45° is formed by the [100] and [1-10] directions of the monoclinic unit cell.

Polymorphism of Two-Dimensional Cyanine Dye J-Aggregates and Its Genesis: Fluorescence Microscopy and Atomic Force Microscopy Study.

Polymorphic J-aggregates of monomethine cyanine dye 3,3'-di(γ-sulfopropyl)-5,5'-dichlorotiamonomethinecyanine (TC) have been studied by fluorescence optical microscopy (FOM) and by atomic force microscopy (AFM). The in situ FOM observations in a solution drop distinguish two J-aggregate morphology classes: flexible strips and rigid rods. The AFM imaging of dried samples reveals a strong J-aggregate structural rearrangement under adsorption on a mica surface with the strips self-folding and the rods squashing into rectangular bilayers and much deeper destruction.