A highly efficient open-shell singlet luminescent diradical with strong magnetoluminescence properties.

Developing open-shell singlet (OS) diradicals with high luminescent properties and exceptional single-molecule magnetoluminescence (ML) performance is extremely challenging. Herein, we propose a concept to enhance luminescent efficiency by adjusting the donor conjugation of OS diradicals, thereby achieving a highly luminescent diradical, DR1, with outstanding stability and making it a viable option for use in the emitting layer of organic light-emitting diodes (OLEDs). More importantly, the 0.5 wt%-DR1 doped film demonstrates significant single-molecule magnetoluminescence (ML) properties. A giant ML value of 210% is achieved at a magnetic field of 7 T, showing the great potential of DR1 in magneto-optoelectronic devices.

A Highly Luminescent Metallo-Supramolecular Radical Cage.

Luminescent metal-radicals have recently received increasing attention due to their unique properties and promising applications in materials science. However, the luminescence of metal-radicals tends to be quenched after formation of metallo-complexes. It is challenging to construct metal-radicals with highly luminescent properties. Herein, we report a highly luminescent metallo-supramolecular radical cage (LMRC) constructed by the assembly of a tritopic terpyridinyl ligand RL with tris(2,4,6-trichlorophenyl)methyl (TTM) radical and Zn2+. Electrospray ionization-mass spectrometry (ESI-MS), traveling-wave ion mobility-mass spectrometry (TWIM-MS), X-ray crystallography, electron paramagnetic resonance (EPR) spectroscopy, and superconducting quantum interference device (SQUID) confirm the formation of a prism-like supramolecular radical cage. LMRC exhibits a remarkable photoluminescence quantum yield (PLQY) of 65%, which is 5 times that of RL; meanwhile, LMRC also shows high photostability. Notably, significant magnetoluminescence can be observed for the high-concentration LMRC (15 wt % doped in PMMA film); however, the magnetoluminescence of 0.1 wt % doped LMRC film vanishes, revealing negligible spin-spin interactions between two radical centers in LMRC.

A Highly Stable Organic Luminescent Diradical.

It is very challenging to obtain stable room-temperature luminescent open-shell singlet diradicals. Herein we report the first stable Müller's hydrocarbon TTM-PhTTM with luminescent properties. Variable-temperature electron paramagnetic resonance spectroscopy measurements and theoretical calculations show that TTM-PhTTM has an open-shell singlet ground state with a diradical character of 90 %. Because of a small singlet-triplet energy gap, the open-shell singlet ground state can be thermally excited to a triplet state. TTM-PhTTM shows room-temperature deep-red emission in various solutions. Unusually high stability of TTM-PhTTM was also observed owing to effective steric hindrance and spin delocalization. Our results are beneficial to the rational design and discovery of more stable luminescent diradical materials.

A simple organic multi-analyte fluorescent prober: One molecule realizes the detection to DNT, TATP and Sarin substitute gas.

The detections of explosives and chemical warfare agents (CWAs) are always important for global security. In this study, a simple donor (D)- acceptor (A) type small organic fluorescent triazole-based molecule (T1) is reported. T1 is composed of a central 4H-1, 2, 4-triazole (TAZ) "core" and three external triphenylamine (TPA) groups. Its spin-coating films can realize the multi-analyte fluorescent prober to detect DNT (2, 4-dinitrotoluene), hydrogen peroxide (H2O2, the substitute for triacetone triperoxide (TATP)) and diethylchlorophosphate (DCP, the substitute for Sarin) vapors. Additionally, the combination of the triple sensing mechanism in the different channels affords three distinct sets of output-signal responses, these three hazardous compounds could be identified rapidly with high sensitivity and selectivity: fluorescence turn-off response to DNT, fluorescence turn-on response to H2O2 and fluorometric-colorimetric dual-channel response to DCP. T1 fluorescent probe is highly advantageous for concurrently monitoring various hazardous target substances and simultaneously possessing the desirable sensitivity and selectivity, excellent reusability. Hereby, this study provides a prototype method to build novel multifunctional fluorescent probes to explosives and CWAs.

Polymer Light Emitting Diodes with Doublet Emission.

Organic light-emitting radicals have developed rapidly due to their unique doublet emission and great potential in display technology. Although some organic light-emitting diodes (OLEDs) exploiting small-molecular radicals as the emitters have been reported, there is no report about the polymer-radical-based OLEDs until now. Herein, a kind of polymer radical, PS-CzTTM, is adopted as the emitter to fabricate solution-processed OLEDs. A maximum external quantum efficiency of 3.0% is achieved for a deep-red device with an emissive layer of PS-CzTTM lightly doped in 2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1H-benzimidazole) (TPBi). Temperature-dependent time-resolved photoluminescent spectra and transient electroluminescence of radical emitters and devices are first measured. The results demonstrate that the emission channels for both thin films and devices are from the transition of doublet excitons, indicating that the unique doublet emission mechanism of radicals is maintained in PS-CzTTM films and PS-CzTTM-based OLEDs.

Understanding the luminescent nature of organic radicals for efficient doublet emitters and pure-red light-emitting diodes.

The doublet-spin nature of radical emitters is advantageous for applications in organic light-emitting diodes, as it avoids the formation of triplet excitons that limit the electroluminescence efficiency of non-radical emitters. However, radicals generally show low optical absorption and photoluminescence yields. Here we explain the poor optical properties of radicals based on alternant hydrocarbons, and establish design rules to increase the absorption and luminescence yields for donor-acceptor-type radicals. We show that non-alternant systems are necessary to lift the degeneracy of the lowest energy orbital excitations; moreover, intensity borrowing from an intense high-lying transition by the low-energy charge-transfer excitation enhances the oscillator strength of the emitter. We apply these rules to design tris(2,4,6-trichlorophenyl)methyl-pyridoindolyl derivatives with a high photoluminescence quantum yield (>90%). Organic light-emitting diodes based on these molecules showed a pure-red emission with an over 12% external quantum efficiency. These insights may be beneficial for the rational design and discovery of highly luminescent doublet emitters.

Highly Efficient Fluorescent Organic Light-Emitting Devices Using a Luminescent Radical as the Sensitizer.

In traditional fluorescent organic light-emitting diodes (OLEDs), the upper limit of internal quantum efficiency (IQE) is only 25% because 75% of triplet excitons created on the fluorescent dyes are nonluminous. Here luminescent radicals are proposed as the sensitizer. Under ideal conditions, electrons and holes first recombine on the sensitizer molecule to create doublet excitons, then through energy transfer to generate singlet excitons on the fluorescent dye, and, finally, via radiative decay to emit light. The upper limit of IQE can theoretically reach 100%. As an example, the maximum external quantum efficiency (EQE) of a fluorescent OLED sensitized by a luminescent radical, TTM-1Cz, has reached 8.1%, which is much higher than the upper limit of EQE of traditional fluorescent OLEDs. Our results suggest a new route to realize highly efficient fluorescent OLEDs.

Radical-Based Organic Light-Emitting Diodes with Maximum External Quantum Efficiency of 10.6.

A new luminescent radical, tris-2,4,6-trichlorophenylmethyl-1,5-diazarcarbazole (TTM-DACz), was synthesized and characterized. The photoluminescence quantum yield of TTM-DACz in solid 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene matrix film (5 wt %) is as high as 57.0%. Organic light-emitting diodes (OLEDs) employing TTM-DACz as the emitter were fabricated. By rational design of the device structure and host-guest doping system, external quantum efficiency (EQE) of up to 10.6% of the optimized device with a red CIE chromaticity of (0.62, 0.36) was obtained, which is among the highest values for red OLEDs using nonphosphorescent materials as the emitters. This work will accelerate the development of luminescent radical materials for high-performance OLEDs.