Synthesis of 2,5,8-Tris(1-phenyl-1 H -benzo[ d ]imidazol-2-yl)benzo[1,2- b :3,4- b ':5,6- b ″] Trithiophenes and Their Spontaneous Orientation Polarization in Thin Films.

To investigate the relationship between molecular structures and spontaneous orientation polarization (SOP) in organic thin films, 2,5,8-tris(1-phenyl-1 H -benzo[ d ]imidazol-2-yl)benzo[1,2- b :3,4- b ':5,6- b ″] trithiophene (TPBTT) and its ethyl derivative ( m -ethyl-TPBTT) were synthesized. Variable angle spectroscopic ellipsometry and two-dimensional grazing-incidence wide-angle X-ray scattering showed that the vacuum-deposited films of TPBTT and m -ethyl-TPBTT had a higher degree of molecular orientation parallel to the substrate compared with that of prototypical 2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1- H -benzimidazole) (TPBi) due to the larger π-conjugated benzotrithiophene core. However, TPBTT films showed a lower SOP of +54.4 mV/nm than did the TPBi film (+77.3 mV/nm), indicating that the molecular orientation alone did not determine the SOP. In contrast, m -ethyl-TPBTT showed a larger SOP of +104.0 mV/nm in the film. Quantum chemical calculations based on density functional theory suggested that the differences in the stable molecular conformation and the permanent dipole moments between TPBTT and m -ethyl-TPBTT caused the differences in SOP. These results suggest that the simultaneous control of the orientational order and conformation of the molecules is important to achieving a large SOP in films.