Highly efficient organic LEDs made by solution processing are reported. It is shown that the dendritic architecture (see Figure) can be used to solubilize luminescent chromophores and form uniform films of blends. The simple device structures containing a light‐emitting chromophore are amongst the most efficient solution‐processed devices reported. Thanks to this technique, the inkjet printing of phosphorescent materials becomes feasible.

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Reactions of 1,4-dimethyl-1,4,7-triazacyclononane (L1a) and 1,4-diisopropyl-1,4,7-triazacyclononane (L1b) to form 1-aminopropyl-4,7-di-R-1,4,7-triazacyclononane [R = Me (H2L3a) or Pri (H2L3b)] and 1-(2-aminobenzyl)-4,7-di-R-1,4,7-triazacyclononane [R = Me (H2L5a) or Pri (H2L5b)] are reported. Reaction of H2L3a and H2L5a with [Ti(NMe2)2Cl2] gives the ansa-linked macrocycle-imido complexes [Ti(kappa 4-L3a)Cl2] (5a) and [Ti(kappa 4-L5a)Cl2] (6a), respectively, and NHMe2. Reaction of H2L3a with [Ti(NBut)Cl2(py)3] gives [Ti(NBut)(kappa 3-H2L3a)Cl2] (7), which possesses a pendant alkylamine group that does not undergo amine/tert-butylimido group exchange to give 5a and ButNH2. However, reaction of H2L3b and H2L5b with [Ti(NBut)Cl2(py)3] does give amine/tert-butylimido group exchange to form [Ti(kappa 4-L3b)Cl2] (5b), [Ti(kappa 4-L5b)Cl2] (8b), and ButNH2. The compounds 5a,b and 6a,b are isolobal analogues of group 4 ansa-metallocene complexes and relatives of titanium cyclopentadienyl-amido constrained geometry olefin polymerization catalysts. Reaction of 5b with AgOTf affords [Ti(kappa 4-L3b)(OTf)Cl] (8) as the major product, the crystal structure of which has been determined. Alkylation of 6b by RLi gives the dialkyl derivatives [Ti(kappa 4-L5b)(R)2] [R = Me (9) or CH2SiMe3 (10)]. The ethylene polymerization capability of the compounds 5a,b, 6a,b, and 10 in the presence of methylaluminoxane has been determined and compared to that of [Ti(NBut)(kappa 3-L1a,b)Cl2] (11a,b); in all instances, low yields of high-molecular-weight polymer are obtained.

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