Photoinduced arylation of chloroarenes in flow: synthesis of unsymmetrical biaryls.

A photoflow method is presented for a radical-based coupling of unactivated arenes and aryl chlorides. The process proceeded smoothly at ambient temperature under metal-free conditions. Of note is that the reaction conditions are fine-tuned for chloroarenes with different electronic properties. While the reactivity profile of aryl chlorides is generally known to be inferior to those of the corresponding iodides and bromides, we demonstrate that the title protocol is efficient in converting readily available and inexpensive chloroarenes into unsymmetrical biaryl products.

Mechanism and kinetics for both thermal and electrochemical reduction of N2 catalysed by Ru(0001) based on quantum mechanics.

The conversion of N2(g) to NH3(g) is an important industrial process that plays a vital role in sustaining the current human population. This chemical transformation relies heavily on the Haber-Bosch process (N2 thermal reduction, N2TR), which requires enormous quantities of energy (2% of the world supply) and extreme conditions (200 atm and 500 °C). Alternatively, N2(g) can be reduced to NH3(g) through electrochemical means (N2ER), which may be a less energy intensive and lower-capital approach since the H atoms come from H2O not H2. However, N2ER efficiency is far from satisfactory. In order to provide the basis for developing a new generation of energy efficient processes, we report the detailed atomistic mechanism and kinetics for N2ER on Ru(0001) along with a comparison to N2TR. We obtained these results using a new electrochemical model for quantum mechanics (QM) calculations to obtain free energy surfaces for all plausible reaction pathways for N2ER under a constant electrode potential of 0.0 VSHE. For both processes, the elementary steps involve several steps of breaking of the NN bonds, hydrogenation of surface N2HX or NHX, and NH3 release. We find similar energetics for the NN cleavage steps for both systems. However, the hydrogenation steps are very different, leading to much lower free energy barriers for N2ER compared to N2TR. Thus, N2ER favors an associative route where successive hydrogen atoms are added to N2 prior to breaking the NN bonds rather than the dissociative route preferred by N2TR, where the NN bonds are broken first followed by the addition of Hs. Our QM results provide the detailed free energy surfaces for N2ER and N2TR, suggesting a strategy for improving the efficiency of N2ER.

Exciplex Organic Light-Emitting Diodes with Nearly 20% External Quantum Efficiency: Effect of Intermolecular Steric Hindrance between the Donor and Acceptor Pair.

Exciplex emitters have emerged as an important class of thermally activated delayed fluorescence (TADF) materials for highly efficient OLEDs. A TADF exciplex emitter requires an intermolecular donor/acceptor pair. We have synthesized a bipolar donor-type material, DPSTPA, which was used to pair with known acceptor materials (2CzPN, 4CzIPN, or CzDBA). The OLEDs based on the exciplex emitters, DPSTPA/X, where X = 2CzPN and CzDBA, give green and orange-red colors with record-high external quantum efficiencies (EQEs) of 19.0 ± 0.6 and 14.6 ± 0.4%, respectively. In contrast, the exciplex pair DPSTPA/4CzIPN gave a very low photoluminescence quantum yield (PLQY) and a very low EQE value of the device. The DFT calculations indicate that the intermolecular distance between the donor and the acceptor plays a key factor for the PLQY and EQE. The observed low PLQY and the poor device performance for the DPSTPA/4CzIPN pair are probably because of the relatively long distance between the DPSTPA and 4CzIPN in the thin film caused by the four congested carbazole (Cz) groups of 4CzIPN, which effectively block the interaction of the nitrile acceptor with the triphenylamino donor of DPSTPA.