Recently, thermally activated delayed fluorescence (TADF) materials have received increasing attention as effective emitters for organic light-emitting diodes (OLEDs). However, most of them are usually employed as dopants in a host material. In this report, carbazole dendrimers with a triphenyl-s-triazine core are reported, which are the first solution-processable, non-doped, high-molecular-weight TADF materials. The dendrimers were obtained by a new and facile synthetic route using the tert-butyldimethylsilyl moiety as a protecting group. All dendrimers showed TADF in toluene. Measurements of the temperature-dependent luminescence lifetime revealed that spin-coated neat films also showed TADF with moderate quantum yields. OLED devices incorporating these dendrimers as spin-coated emitting layers gave external quantum efficiencies of up to a 3.4 %, which suggests that this device is harvesting triplet excitons. This result indicates that carbazole dendrimers with attached acceptors are potential TADF materials owing to their polarized electronic structure (with HOMO-LUMO separation).

A relationship between the size of metal particles and their catalytic activity has been established over a nanometer scale (2-10 nm). However, application on a subnanometer scale (0.5-2 nm) is difficult, a possible reason being that the activity no longer relies on the size but rather the geometric structure as a cluster (or superatomic) compound. We now report that the catalytic activity for the oxygen reduction reaction (ORR) significantly increased when only one atom was removed from a magic number cluster composed of 13-platinum atoms (Pt13). The synthesis with an atomic-level precision was successfully achieved by using a dendrimer ligand as the macromolecular template strictly defining the number of metal atoms. It was quite surprising that the Pt12 cluster exhibited more than 2-fold catalytic activity compared with that of the Pt13 cluster. ESI-TOF-mass and EXAFS analyses provided information about the structures. These analyses suggested that the Pt12 has a deformed coordination, while the Pt13 has a well-known icosahedral atomic coordination as part of the stable cluster series. Theoretical analyses based on density functional theory (DFT) also supported this idea. The present results suggest potential activity of the metastable clusters although they have been "missing" species in conventional statistical synthesis.

A new synthetic route for carbazole dendrimers was discovered using the copper-catalyzed N-arylation reaction. This synthetic route allowed synthesizing the fourth generation carbazole dendrimer and several derivatives for the first time. The crystal structure, Mark-Houwink-Sakurada plots, and UV-vis and fluorescence studies showed that the dendritic carbazole backbone has a rigid and highly twisted structure. From the measurement of the redox potential of the ferrocene derivatives, the IR spectra of the benzophenone derivatives, and complexation behavior of the phenylazomethine derivatives, the inductive electron-withdrawing effect of the carbazole dendron was revealed. This suggested that the summation of this electron withdrawal from each layer may produce a potential gradient such that the outer layer is electron-rich and the inner layer is electron-poor in the carbazole dendron. By assignment of the (1)H and (13)C NMR spectra of the dendron, the existence of this kind of potential gradient was proved. Overall, these data show the pi-polarization substituent effect of the carbazole unit, and their summation determines the potential gradient in the repeating dendritic structure of the carbazole dendrimer.

New solution processable and laminatable terminally modified carbazole-triazine thermally activated delayed fluorescence (TADF) dendrimers are reported. An OLED device with fully solution processed organic layers exhibited an external quantum efficiency of up to 9.4% at 100 cd m.

Thermally activated delayed fluorescence (TADF) materials emerged as promising light sources in third generation organic light-emitting diodes (OLED). Much effort has been invested for the development of small molecular TADF materials and vacuum process-based efficient TADF-OLEDs. In contrast, a limited number of solution processable high-molecular weight TADF materials toward low cost, large area, and scalable manufacturing of solution processed TADF-OLEDs have been reported so far. In this context, we report benzophenone-core carbazole dendrimers (GnB, n = generation) showing TADF and aggregation-induced emission enhancement (AIEE) properties along with alcohol resistance enabling further solution-based lamination of organic materials. The dendritic structure was found to play an important role for both TADF and AIEE activities in the neat films. By using these multifunctional dendritic emitters as non-doped emissive layers, OLED devices with fully solution processed organic multilayers were successfully fabricated and achieved maximum external quantum efficiency of 5.7%.