s-Indacene Revisited: Modular Synthesis and Modulation of Structures and Molecular Orbitals of Hexaaryl Derivatives.

Though s-indacene is an intriguing antiaromatic hydrocarbon of 12 π-electrons, it has been underrepresented due to the lack of efficient and versatile methods to prepare stable derivatives. Herein we report a concise and modular synthetic method for hexaaryl-s-indacene derivatives bearing electron-donating/-accepting groups at specific positions to furnish C2h-, D2h-, and C2v-symmetric substitution patterns. We also report the effects of substituents on their molecular structures, frontier molecular orbital (MO) levels, and magnetically induced ring current tropicities. Both theoretical calculations and X-ray structure analyses indicate that the derivatives of the C2h-substitution pattern adopt different C2h structures with significant bond length alternation depending on the electronic property of the substituents. Due to the nonuniform distribution of the frontier MOs, their energy levels are selectively modulated by the electron-donating substituents. This leads to the inversion of the HOMO and HOMO-1 sequences with respect to those of the intrinsic s-indacene as theoretically predicted and experimentally proven by the absorption spectra at visible and near-infrared regions. The NICS values and the 1H NMR chemical shifts of the s-indacene derivatives indicate their weak antiaromaticity. The different tropicities are explained by the modulation of the HOMO and HOMO-1 levels. In addition, for the hexaxylyl derivative, weak fluorescence from the S2 excited state was detected due to the large energy gap between the S1 and S2 states. Notably, an organic field-effect transistor (OFET) fabricated using the hexaxylyl derivative exhibited moderate hole carrier mobility, a result which opens the door for optoelectronic applications of s-indacene derivatives.

Triarylamine-Pyridine-Carbonitriles for Organic Light-Emitting Devices with EQE Nearly 40.

Highly efficient thermally activated delayed fluorescence (TADF) molecules are in urgent demand for solid-state lighting and full-color displays. Here, the design and synthesis of three triarylamine-pyridine-carbonitrile-based TADF compounds, TPAPPC, TPAmPPC, and tTPAmPPC, are shown. They exhibit excellent photoluminescence quantum yields of 79-100% with small ΔEST values, fast reverse intersystem crossing (RISC), and high horizontal dipole ratios (Θ//  = 86-88%) in the thin films leading to the enhancement of device light outcoupling. Consequently, a green organic light-emitting diode (OLED) based on TPAmPPC shows a high average external quantum efficiency of 38.8 ± 0.6%, a current efficiency of 130.1 ± 2.1 cd A-1 , and a power efficiency of 136.3 ± 2.2 lm W-1 . The highest device efficiency of 39.8% appears to be record-breaking among TADF-based OLEDs to date. In addition, the TPAmPPC-based device shows superior operation lifetime and high-temperature resistance. It is worth noting that the TPA-PPC-based materials have excellent optical properties and the potential for making them strong candidates for TADF practical application.