Structure and dynamics of a discotic liquid-crystalline charge-transfer complex

The structure of the charge-transfer complex hexakis(n-hexyloxy)triphenylene-2,4,7-trinitro-9-fluorenone (HAT6-TNF) has been characterized by neutron scattering, X-ray diffraction (XRD), optical microscopy, and dielectric relaxation spectroscopy (DRS). On the basis of these data and the 1:1 stoichiometry, a consistent structure for the complex is proposed. This structure differs markedly from structures previously proposed for similar materials, because the TNF molecules are found to be situated between the discotic columns rather than sandwiched between the discotic molecules of a given column. The addition of TNF to HAT6 is found to stiffen the structure, and quasi-elastic neutron scattering shows that the local dynamics of the discotic molecules in HAT6-TNF is slowed by the presence of the TNF molecules. This scenario is consistent with the observation of two VFT-type (VFT=Vogel-Fulcher-Tamman) dielectric relaxation processes that relate to the columnar glass transition and a polyethylene-like hindered glass transition originating from the nano-phase-separated fraction of the aliphatic tails.