Control of orientation for carbazole group in comb copolymers arranged by method of organized molecular films

We investigated the molecular orientation of organized molecular films with regard to solid‐state structures for newly synthesized comb copolymers with N‐vinylcarbazole (NVCz) by in‐plane and out‐of plane X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and atomic force microscopy (AFM). In the bulk state, hydrogenated and fluorinated comb copolymers form side‐chain crystals for a two‐dimensional lattice spacing of 4.2 and 5.0 Å, respectively. The findings suggest that the carbazole rings in the main‐chain are arranged in opposition to each other. From the results of the DSC measurement, sharp‐shaped melting peaks appear on the relatively lower temperature side of the thermograms. This result supports the formation of side‐chain crystals in the synthesized comb copolymers. These monolayers of the copolymers on the water surface were extremely condensed, except for the fluorocarbon:NVCz = 1:1 copolymer. From the in‐plane XRD measurement of multilayers on solids, the changes in the two‐dimensional lattice structure of fluorinated comb copolymer films containing NVCz units, as opposed to their bulk state, were confirmed. It seems that these structural changes are caused by the stronger π–π interaction between the carbazole rings rather than the van der Waals interaction between fluorocarbons. Copyright © 2007 John Wiley & Sons, Ltd.