Solid-State Properties and Spectroscopic Analysis of Thin-Film TPBi

We characterized the prominent electron transport layer 2,2′,2″-(1,3,5-benzinetriyl)-tris­(1-phenyl-1-H-benzimidazole) (TPBi) via single-crystal X-ray diffraction, grazing incidence X-ray diffraction (GIXRD), infrared reflection absorption spectroscopy (IRRAS), and quantum mechanical calculations. The crystals generated via vapor diffusion are of the orthorhombic space group Pbca , with a unit cell [a = 19.3935(2) b = 12.81750(10) c = 28.5610(3) Å] containing eight TPBi molecules, and screw axes and glide planes along all three crystallographic axes. Thin-film analysis becomes viable with unit cell and symmetry data, and GIXRD measurements, which demonstrate that when the amorphous TPBi thin films are annealed, the molecules preferentially orient with the a–b crystallographic face exposed at the surface and with the central benzene rings oriented 29° from the surface normal. Changes in vibrational modes at the surface, studied via infrared reflection absorption spectroscopy (IRRAS), concur with the X-ray based assignments. A minor conformer of TPBi with C 3 symmetry was also identified via computational methods, appearing 0.95 kcal/mol higher in energy at the MP2/6-31G*//B3LYP/6-31G* level of theory. The combined structural insight allows fine-tuning of a device structure for organic light-emitting diodes (OLEDs) and organic photovoltaic applications.