Ultra-fast triplet-triplet-annihilation-mediated high-lying reverse intersystem crossing triggered by participation of nπ*-featured excited states.

The harvesting of 'hot' triplet excitons through high-lying reverse intersystem crossing mechanism has emerged as a hot research issue in the field of organic light-emitting diodes. However, if high-lying reverse intersystem crossing materials lack the capability to convert 'cold' T1 excitons into singlet ones, the actual maximum exciton utilization efficiency would generally deviate from 100%. Herein, through comparative studies on two naphthalimide-based compounds CzNI and TPANI, we revealed that the 'cold' T1 excitons in high-lying reverse intersystem crossing materials can be utilized effectively through the triplet-triplet annihilation-mediated high-lying reverse intersystem crossing process if they possess certain triplet-triplet upconversion capability. Especially, quite effective triplet-triplet annihilation-mediated high-lying reverse intersystem crossing can be triggered by endowing the high-lying reverse intersystem crossing process with a 3ππ*→1nπ* character. By taking advantage of the permanent orthogonal orbital transition effect of 3ππ*→1nπ*, spin-orbit coupling matrix elements of ca. 10 cm-1 can be acquired, and hence ultra-fast mediated high-lying reverse intersystem crossing process with rate constant over 109 s-1 can be realized.

An Ultraviolet Thermally Activated Delayed Fluorescence OLED with Total External Quantum Efficiency over 9.

Owing to the difficulty in acquiring compounds with combined high energy bandgaps and lower-lying intramolecular charge-transfer excited states, the development of ultraviolet (UV) thermally activated delayed fluorescence (TADF) materials is quite challenging. Herein, through interlocking of the diphenylsulfone (PS) acceptor unit of a reported deep-blue TADF emitter (CZ-PS) by a dimethylmethylene bridge, CZ-MPS, a UV-emissive TADF compound bearing a shallower LUMO energy level and a more rigid structure than those of CZ-PS is achieved. This represents the first example of a UV-emissive TADF compound. Organic light-emitting diode (OLED) using CZ-MPS as the guest material can emit efficient UV light with emission maximum of 389 nm and maximum total external quantum efficiency (EQEmax ) of 9.3%. Note that this EQEmax value is twice as high as the current record EQEmax (4.6%) for UV-OLEDs. This finding may shed light on the molecular design strategy for high-performance UV-OLED materials.

Acquiring High-Performance Deep-Blue OLED Emitters through an Unexpected Blueshift Color-Tuning Effect Induced by Electron-Donating -OMe Substituents.

A series of blue-emissive 7-(diphenylamino)-4-phenoxycoumarin derivatives bearing -CF3 , -OMe, or -N(Me)2 substituents on the phenoxy subunit were synthesized. Although both the -CF3 and -N(Me)2 modifications were found to trigger redshifted fluorescence, the -OMe substitution was demonstrated to exert an unexpected blueshift color-tuning effect toward the deep-blue region. The reason is that the moderate electron-donating -OMe group can endow coumarins with unaltered HOMO but elevated LUMO energy levels. Moreover, the -OMe substitution was found to be beneficial to the thermal stability of these coumarins. Therefore, the trimethoxy-substituted objective compound can act as a high-performance deep-blue organic light-emitting diode (OLED) emitter, and OLED based on it emits deep-blue light with CIE coordinates of (0.148, 0.084), maximum luminance of 7800 cd m-2 , and maximum external quantum efficiency of 5.1 %. These results not only shed light on the molecular design strategy for high-performance deep-blue OLED emitters through color-tuning, but also show the perspective of coumarin derivatives as deep-blue OLED emitters.

Exploring the mechanism of F282L mutation-caused constitutive activity of GPCR by a computational study.

G-protein-coupled receptors (GPCRs) are important drug targets and generally activated by ligands. However, some experiments found that GPCRs also give rise to constitutive activity through some mutations (viz., CAM), which are usually associated with different kinds of diseases. However, the mechanisms of CAMs and their roles in interactions with drug-ligands are unclear in experiments. Herein, we used microsecond molecular dynamics simulations to study the effect of one important F282L mutation on ß2AR in order to address the questions above. With the aid of principle component and correlation analysis, our results revealed that the F282L mutation could increase the instability of the overall structure, increase the dramatic fluctuations of NPxxY and extracellular loops, and decrease restraint of the helices through weakening interhelical H-bonding and correlations between residues, which could partly contribute to the constitutive activity reported by the experiments. The observations from the protein structure network (PSN) analysis indicate that the mutant exhibits less information flow than the wild ß2AR and weakens the role of TM5 and TM6 in the signal transmission, but it enhances the impact of TM3 on the orthosteric pathway and TM4 on the allosteric one. In addition, the results from the virtual screening reveal that the mutant prefers to select agonists rather than antagonists, similar to the active state but opposite of the inactive state, further confirming that the F282L mutation advances the activation of ß2AR. Our observations provide valuable information for understanding the mechanism of the mutation-caused constitutive activity of GPCR and related drug-design.