2,7-Bis(diarylamino)-9,9-dimethylfluorenes as Hole-Transport Materials for Organic Light-Emitting Diodes

2,7‐Bis(p‐methoxyphenyl‐m′‐tolylamino)‐9,9‐dimethylfluorene (1′), 2,7‐bis(phenyl‐m′‐tolylamino)‐9,9‐dimethylfluorene (2′) and 2,7‐bis(p‐fluorophenyl‐m′‐tolylamino)‐9,9‐dimethylfluorene (3′) have been synthesized using the palladium‐catalyzed reaction of the appropriate diarylamines with 2,7‐dibromo‐9,9‐dimethylfluorene. These molecules have glass‐transition temperatures 15–20 °C higher than those for their biphenyl‐bridged analogues, and are 0.11–0.14 V more readily oxidized. Fluorescence spectra and fluorescence quantum yields for dimethylfluorene‐bridged and biphenyl‐bridged species are similar, but the peaks of the absorption spectra of 1′–3′ are considerably red‐shifted relative to those of their biphenyl‐bridged analogues. Time‐of‐flight hole mobilities of 1′–3′/polystyrene blends are in a similar range to those of the biphenyl‐bridged analogues. Analysis according to the disorder formalism yields parameters rather similar to those for the biphenyl species, but with somewhat lower zero‐field mobility values. Density functional theory (DFT) calculations suggest that the enforced planarization of the fluorene bridge leads to a slightly larger reorganization energy for the neutral/cation electron‐exchange reaction than in the biphenyl‐bridged system. Organic light‐emitting diodes have been fabricated using 1′–3′/polystyrene blends as the hole‐transport layer and tris(8‐hydroxy quinoline)aluminium as the electron‐transport layer and lumophore. Device performance shows a correlation with the ionization potential of the amine materials paralleling that seen in biphenyl‐based systems, and fluorene species show similar performance to biphenyl species with comparable ionization potential. Three 2,7‐bis(diarylamino)‐9,9‐dimethylfluorenes have been synthesized (see Figure). Compared to their biphenyl‐bridged analogues, glass‐transition temperatures are higher and ionization potentials are lower. Hole mobilities are in a similar range for fluorene and biphenyl species, but lower zero‐field mobilities are found for the former. Fluorene and biphenyl species with similar ionization potential show similar behavior in light‐emitting diodes.