The first series of monodisperse glass-forming, nematic oligofluorenes was synthesized following a divergent-convergent approach. Both chain length and pendant structure were found to affect solid morphology and phase transition temperatures. With optimized structural parameters, a T-g close to 150 degreesC and a T-c beyond 375 degreesC were achieved. This material class is characterized by its ability to form monodomain glassy nematic films via spin-coating, thermal annealing at 10 to 20 degreesC above T-g for 15-30 min, and cooling to room temperature without encountering crystallization. The absorption and emission dichroic ratios of 80-90-nm-thick films increase from 7 to 17 with an increasing molecular aspect ratio, while the photoluminescence quantum yield varies erratically from 43 to 60%. Superior stability of emissive color and of emission dichroic ratio and that against thermally activated crystallization were also demonstrated through prolonged heating of a film at 10 degreesC above T-g under argon.
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