High-efficiency triplet-triplet annihilation upconversion microemulsion with facile preparation and decent air tolerance.

Current research of triplet-triplet annihilation upconversion (TTA-UC) faces difficulty such as overuse of organic solvents and quenching of excited triplet sensitizers by molecular oxygen. Herein, we propose an efficient and facile preparation strategy of TTA-UC microemulsion to overcome these issues. With simple device and short preparation process, air-stable TTA-UC with a high upconversion efficiency of 16.52% was achieved in microemulsion coassembled from TritonX114, tetrahydrofuran and upconverting chromophores (platinum octaethyl-porphyrin and 9,10-diphenylanthracene). This is comparable to the highest UC efficiency ever reported for TTA-UC microemulsion systems. The excellent UC performance of TX114-THF could be attributed to two perspectives. Firstly, small-size micelle accommodated chromophores up to high concentrations in organic phase, which promoted efficient molecular collision. Additionally, high absorbance at 532 nm ensured full use of excitation light, getting more long wavelength photons involved in the TTA-UC process. Moreover, air-stable TTA-UC also performed well in microemulsion with various surfactants, including nonionic surfactants (Tween 20, Tween 80, Triton X-110, Triton X-114), ionic surfactants (sodium dodecyl sulfate, cetyltrimethyl ammonium bromide) and block copolymers (pluronic F127, pluronic P123), through three conjectural assembly models according to the structural characteristics of surfactant molecules (concentrated, uncompacted and scattered). These discoveries could provide estimable reference for selection of surfactants in relevant fields of TTA-UC.

Improving the Efficiency and Stability of MAPbI3 Perovskite Solar Cells by Dipeptide Molecules.

Passivating the electronic defects of metal halide perovskite is regarded as an effective way to improve the power conversion efficiency (PCE) of perovskite solar cells (PVSCs). Here, a series of dipeptide molecules with abundant ─C═O, ─O─ and ─NH functional groups as defects passivators for perovskite films are employed. These dipeptide molecules are utilized to treat the surface of prototype methyl ammonium lead iodide (MAPbI3) films and the corresponding PVSCs exhibit enhanced photovoltaic performance and ambient stability, which can be ascribed to: 1) the ─C═O and ─O─ can interact with the undercoordinated Pb2+ ions and the ─NH groups can form hydrogen bonds with the I- ions, passivating the defects in perovskite film and reducing charge recombination in PVSCs; 2) the long alkyl chain of dipeptide molecules increases the hydrophobicity of the perovskite surface and thus enhance the stability of PVSCs. The passivated MAPbI3-based PVSCs exhibit a champion PCE of 20.3% and retain 60% of the initial PCE after 1000 h. It is believed that the defects passivation engineering using polypeptide moleculars can be applied in other perovskite compositions for high device efficiency and stability.

Macrocyclic Engineering of Thermally Activated Delayed Fluorescent Emitters for High-Efficiency Organic Light-Emitting Diodes.

Several thermally activated delayed fluorescence (TADF) materials have been studied and developed to realize high-performance organic light-emitting diodes (OLEDs). However, TADF macrocycles have not been sufficiently investigated owing to the synthetic challenges, resulting in limited exploration of their luminescent properties and the corresponding highly efficient OLEDs. In this study, a series of TADF macrocycles is synthesized using a modularly tunable strategy by introducing xanthones as acceptors and phenylamine derivatives as donors. A detailed analysis of their photophysical properties combined with fragment molecules reveals characteristics of high-performance macrocycles. The results indicate that: a) the ideal structure decreases the energy loss, which in turn reduces the non-radiative transitions; b) reasonable building blocks increase the oscillator strength providing a higher radiation transition rate; c) the horizontal dipole orientation (Θ) of the extended macrocyclic emitters is increased. Owing to the high photoluminescence quantum yields of ≈100% and 92% and excellent Θ of 80 and 79% for macrocycles MC-X and MC-XT in 5 wt% doped films, the corresponding devices exhibit record-high external quantum efficiencies of 31.6% and 26.9%, respectively, in the field of TADF macrocycles.

Photoinduced Radical Persistent Luminescence in Semialiphatic Polyimide System with Temperature and Humidity Resistance.

Organic persistent luminescence (pL) systems with photoresponsive dynamic features have valuable applications in the fields of data encryption, anticounterfeiting, and bioimaging. Photoinduced radical luminescent materials have a unique luminous mechanism with the potential to achieve dynamic pL. It is extremely challenging to obtain radical pL under ambient conditions; on account of it, it is unstable in air. Herein, a new semialiphatic polyimide-based polymer (A0) is developed, which can achieve dynamic pL through reversible conversion of radical under photoexcitation. A "joint-donor-spacer-acceptor" molecular design strategy is applied to effectively modulate the intramolecular charge-transfer and charge-transfer complex interactions, resulting in effective protection of the radical generated under photoirradiation. Meanwhile, polyimide-based polymers of A1-A4 are obtained by doping different amine-containing fluorescent dyes to modulate the dynamic afterglow color from green to red via the triplet to singlet Förster resonance energy-transfer pathway. Notably, benefiting from the structural characteristics of the polyimide-based polymer, A0-A4 have excellent processability, thermal stability, and mechanical properties and can be applied directly in extreme environments such as high temperatures and humidity.

Monopeptide-Based Powder Gelators for Instant Phase-Selective Gelation of Aprotic Aromatics and for Toxic Dye Removal.

Through a combinatorial screening of 35 possible phase-selective monopeptide-based organogelators readily made at low cost, we identified five of them with high gelling ability toward aprotic aromatic solvents in the powder form. The best of them (Fmoc-V-6) is able to instantly and phase-selectively gel benzene, toluene, and xylenes in the presence of water at room temperature at a gelator loading of 6% w/v. This enables the gelled aromatics to be separated by filtration and both aromatics and the gelling material to be recycled by distillation. We also identified Fmoc-I-16 as the best gelator for benzyl alcohol, and the corresponding organogel efficiently removes toxic dye molecules by 82-99% from their highly concentrated aqueous solutions. These efficient removals of toxic organic solvents and dyes from water suggest their promising applications in remediating contaminated water resources.

Controlling the selective synthesis of [2]- and [3]rotaxanes by intermolecular steric hindrance between the macrocyclic hosts.

Two hydrogen-bonded azo-macrocycles with little disparity of the side chains in steric hindrance exhibited a substantial difference in complexation (slow/fast exchange) towards bipyridinium. Inspired by this finding, these macrocycles were applied to efficiently and selectively construct [2]- and [3]rotaxanes through one-pot synthesis. The origin of the selectivity in this novel approach was elucidated by comparing single crystal structures, DFT calculations and stepwise synthesis.

A Dynamic Hydrogen-Bonded Azo-Macrocycle for Precisely Photo-Controlled Molecular Encapsulation and Release.

A light-responsive system constructed from hydrogen-bonded azo-macrocycles demonstrates precisely controlled propensity in molecular encapsulation and release process. A significant decrease in the size of the cavity is observed in the course of the E→Z photoisomerization based on the results from DFT calculations and traveling wave ion mobility mass spectrometry. These macrocyclic hosts exhibit a rare 2:1 host-guest stoichiometry and guest-dependent slow or fast exchange on the NMR timescale. With the slow host-guest exchange and switchable shape change of the cavity, quantitative release and capture of bipyridinium guests is achieved with the maximum release of 68 %. This work underscores the importance of slow host-guest exchange on realizing accurate release of organic cations in a stepwise manner under light irradiation. The light-responsive system established here could advance further design of novel photoresponsive molecular switches and mechanically interlocked molecules.