Structural study of helical polyfluorene under high quasihydrostatic pressure

We report on an x-ray diffraction (XRD) study of helical poly[9,9-bis(2-ethylhexyl)fluorene] (PF2/6) under high quasihydrostatic pressure and show an effect of pressure on the torsion angle (dihedral angle) between adjunct repeat units and on the hexagonal unit cell. A model for helical backbone conformation is constructed. The theoretical position for the most prominent 00l x-ray reflection is calculated as a function of torsion angle. The XRD of high molecular weight PF2/6 (M-n = 30 kg/mol) is measured through a diamond anvil cell upon pressure increase from 1 to 10 GPa. The theoretically considered 00l reflection is experimentally identified, and its shift with the increasing pressure is found to be consistent with the decreasing torsion angle between 2 and 6 GPa. This indicates partial backbone planarization towards a more open helical structure. The h00 peak is identified, and its shift together with the broadening of 00l implies impairment of the ambient hexagonal order, which begins at or below 2 GPa. Previously collected high-pressure photoluminescence data are reanalyzed and are found to be qualitatively consistent with the XRD data. This paper provides an example of how the helical pi-conjugated backbone structure can be controlled by applying high quasihydrostatic pressure without modifications in its chemical structure. Moreover, it paves the way for wider use of high-pressure x-ray scattering in the research of pi-conjugated polymers. DOI: 10.1103/PhysRevE.87.022602