Supramolecular organization of liquid-crystal dimers - bis-cyanobiphenyl alkanes on HOPG by scanning tunneling microscopy.

2D supramolecular organization of a series of six cyanobiphenyls bimesogens deposited on highly oriented pyrolytic graphite (HOPG) is studied by scanning tunneling microscopy (STM). The adsorbates are 1,ω-bis(4-cyanobiphenyl-4'-yl)alkanes (CBnCB) with different lengths of their flexible alkyl spacer (containing from 7 to 12 methylene groups). Microscopic investigations at the molecular resolution allow for detailed analysis of the effect of the alkyl spacer length on the type and the extent of the resulting 2D organization. It was demonstrated that bimesogens with shorter spacers (7 and 8 methylene units) organize in a similar manner characterized by the formation of two types of differently ordered monolayers: dense packed, wherein the molecules are oriented in one direction and ordered into parallel rows (layer structure), or less densely packed where they are organized into a chiral windmill-like structure. For derivatives with longer spacers (ranging from 9 to 12 methylene units) the additional effect of parity of carbon atoms in the spacer (even versus odd) is observed. In this range of the spacer lengths even membered bimesogens are also organized in a typical layer structure. However, odd-membered dimers exhibit a much more complex 2D supramolecular organization with a larger unit cell and a helical arrangement of the molecules. Careful comparison of this structure with the 3D structural data derived from the X-ray diffraction investigations of single crystals indicates that for these bimesogens a clear correlation exists between the observed complex 2D supramolecular organization in the monolayer and the organization in one of the crystallographic planes of the 3D nematic twist-bent phase.