A magnetic field has been utilized for producing highly oriented films of a substituted hexabenzocoronene (HBC). Optical microscopy studies revealed large area HBC monodomains that covered the entire film, while wide-angle X-ray measurements showed that the HBC molecules are aligned with their planes along the applied field. On the basis of this method, solution-processed field-effect transistors (FET) have been constructed with charge carrier mobilities of up to 10(-3) cm2/V.s, which are significantly enhanced with respect to the unaligned material. Exceptionally high mobility anisotropies of 25-75 for current flow parallel and perpendicular to the alignment direction have been measured as a function of the channel length. Atomic force microscopy performed on the FET structures reveals fibril superstructures that are oriented perpendicularly to the magnetic field direction, consisting of molecular columns with a slippage angle of 40 degrees between the molecules. For channel lengths larger than 2.5 mum, the fibrils are smaller than the electrode spacing, which adversely affects the device performance.
The phosphorescence spectra of a series of small oligothiophenes (nT, n = 1-3) incorporating a variety of substituents, end cappers, and functional groups have been recorded for the first time using gated detection in combination with nanosecond excitation in frozen solution at 80 K. The vibrationally resolved emission spectra provide accurate estimates of the T(1) and S(1) levels, and the singlet-triplet energy gap. Theoretical quantum chemical calculations performed at the DFT (B3LYP/6-31G*) level reproduce all experimental trends accurately and provide quantitative description of the S(0)-T(1) energy difference. The geometry relaxation in the excited state shows that the "natural" size of the triplet exciton is about 3-4 thiophene units.
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