Resonance-Induced Dynamic Triplet Exciton Population for Photoactivated Organic Ultralong Room Temperature Phosphorescence.

Dynamically populating triplet excitons under external stimuli is desired to develop smart optoelectronic materials, but it remains a formidable challenge. Herein, we report a resonance-induced excited state regulation strategy to dynamically modulate the triplet exciton population by introducing a self-adaptive N-C═O structure to phosphors. The developed phosphors activated under high-power ultraviolet irradiation exhibited enhanced photoactivated organic ultralong room temperature phosphorescence (PA-OURTP) with lifetimes of up to ∼500 ms. The enhanced PA-OURTP was ascribed to activated N-C═O resonance variation-induced intersystem crossing to generate excess triplet excitons. The excellent PA-OURTP performance and ultralong deactivation time under ambient conditions of the developed materials could function as a reusable recorded medium for time-sensitive information encryption through optical printing. This study provides an effective approach to dynamically regulating triplet excitons and offers valuable guidance to develop high-performance PA-OURTP materials for security printing applications.

Achieving Stimuli-Responsive Amorphous Organic Afterglow in Single-Component Copolymer through Self-Doping.

The development of stimuli-responsive materials with afterglow emission is highly desirable but remains a formidable challenge in a single-component material system. Herein, we propose a strategy to achieve photoactivated afterglow emission in a variety of amorphous copolymers through self-doping, endowed by the synergetic effect of self-host-induced guest sensitization and thermal-processed polymer rigidification for boosting the generation and stabilization of triplet excitons. Upon continuous ultraviolet illumination for regulating the oxygen concentration, a photoactivated afterglow showing increased lifetimes from 0.34 to 867.4 ms is realized. These afterglow emissions can be naturally or quickly deactivated to the pristine state under ambient conditions or heating treatment. Interestingly, programmable and reusable afterglow patterns, conceptual pulse-width indicators, and "excitation-time lock" Morse code are successfully established using stimuli-responsive afterglow polymers as recorded media. These findings offer an avenue to construct a single-component polymeric system with photoactivated organic afterglow features and demonstrate the superiority of stimuli-responsive materials for remarkable applications.

Resonance-Induced Stimuli-Responsive Capacity Modulation of Organic Ultralong Room Temperature Phosphorescence.

Organic ultralong room temperature phosphorescence (OURTP) materials having stimuli-responsive attributes have attracted great attention due to their great potential in a wide variety of advanced applications. It is of fundamental importance but challengeable to develop stimuli-responsive OURTP materials, especially such materials with modulated optoelectronic properties in a controlled manner probably due to the lack of an authentic construction approach. Here, we propose an effective strategy for OURTP materials with controllably regulated stimuli-responsive properties by engineering the resonance linkage between flexible chain and phosphor units. A quantitative parameter to demonstrate the stimuli-responsive capacity is also established by the responsivity rate constant. The designed OURTP materials demonstrate efficient photoactivated OURTP with lifetimes up to 724 ms and tunable responsivity rate constants ranging from 0.132 to 0.308 min-1 upon continuous UV irradiation. Moreover, the applications of stimuli-responsive resonance OURTP materials have been illustrated by the rewritable paper for snapshot and Morse code for multiple information encryption. Our works, which enable the accomplishment of OURTP materials capable of on-demand manipulated optical properties, demonstrate a viable design to explore smart OURTP materials, giving deep insights into the dynamically stimuli-responsive process.

Stable N,N'-Diarylated Dihydrodiazaacene Radical Cations.

Three stable N,N'-diarylated dihydroazaacene radical cations were prepared by oxidation of neutral N,N'-diarylated dihydroazaacenes synthesized via palladium-catalyzed Buchwald-Hartwig aminations of aryl iodides with N,N'-dihydroazaacenes. Both neutral as well as oxidized species were investigated via UV-vis spectroscopy, single crystal analysis, and DFT calculations. All the radical cations are surprisingly stable-their absorption spectra in dichloromethane remain unchanged in ambient conditions for at least 24 hours.

Phosphine Sulfide-Based Bipolar Host Materials for Blue Phosphorescent Organic Light-Emitting Diodes.

Three phosphine sulfide-based bipolar host materials, vizCzPhPS, DCzPhPS, and TCzPhPS, were facilely prepared through a one-pot synthesis in excellent yields. The developed hosts exhibit superior thermal stabilities with the decomposition temperatures (Td) all exceeding 350 °C and the melting temperatures (Tm) over 200 °C. In addition, their triplet energy (ET) levels are estimated to be higher than 3.0 eV, illustrating that they are applicable to serve as hosts for blue phosphorescent organic light-emitting diodes (PhOLEDs). The maxima luminance, current efficiency (CE), power efficiency (PE), and external quantum efficiency (EQE) of 17,223 cd m-2, 36.7 cd A-1, 37.5 lm W-1, and 17.5% are achieved for the blue PhOLEDs hosted by CzPhPS. The PhOLEDs based on DCzPhPS and TCzPhPS show inferior device performance than that of CzPhPS, which might be ascribed to the deteriorated charge transporting balance as the increased number of the constructed carbazole units in DCzPhPS and TCzPhPS molecules would enhance the hole-transporting ability of the devices to a large extent. Our study demonstrates that the bipolar hosts derived from phosphine sulfide have enormous potential applications in blue PhOLEDs, and the quantity of donors should be well controlled to exploit highly efficient phosphine sulfide-based hosts.

Stable Radical Cations of N,N'-Diarylated Dihydrodiazapentacenes.

A series of quinoidal N,N'-diaryldiaza-N,N'-dihydropentacenes (Quino) was prepared in a two-step reaction, starting from quinacridone. Oxidation of Quino furnishes stable radical cations, isoelectronic to the radical anions of the azaacenes, whereas the dicationic species are isoelectronic to neutral azapentacenes. The spectroscopic properties of the diaryldiazapentacenes and their oxidized mono- and dications are equivalent to that of the dianion of tetraazapentacene (TAP), its radical anion and the neutral TAP.

5,7,12,14-Tetrafunctionalized 6,13-Diazapentacenes.

The synthesis, property evaluation, and single crystal X-ray structures of four 5,7,12,14-tetrafunctionalized diazapentacenes are presented. The synthesis of these compounds either starts from tetrabromo-N,N-dihydrodiazapentacene or from a diazapentacene tetraketone. Pd-catalyzed coupling or addition of a lithium acetylide gave the precursors that furnish, after further redox reactions, the diazapentacenes as stable crystalline materials. The performance of the tetraphenyl-substituted compound as n-channel semiconductor was evaluated in organic field effect transistors.

Rational Design of Bipolar Host and Thermally Activated Delayed Fluorescence Materials in Donor-Acceptor Molecular Architecture: A Theoretical Study.

Donor-acceptor (D-A) molecules have drawn massive attention recently in the design of high-performance materials, but the underlying reasons for the magic abilities of D-A architecture in building very different organic semiconductors are still unclear. Here, based on a series of experimentally bipolar host and thermally activated delayed fluorescence (TADF) molecules with the same donor but different acceptor units, it was found that TADF emitters have more effective charge transfer between donor and acceptor units than bipolar host molecules. More efficient conjugation effects between the donor and acceptor units of host materials were identified from the lower dihedral angles of the D-A structure, smaller and even negative charge transfer amount, shorter charge-transfer length, and larger hole-electron overlap extent. These findings with in-depth insights into different interaction models of donor and acceptor units shed important light on the molecular design of TADF emitters and bipolar materials in a D-A architecture.

Enabling robust blue circularly polarized organic afterglow through self-confining isolated chiral chromophore.

Creating circularly polarized organic afterglow system with elevated triplet energy levels, suppressed non-radiative transitions, and effective chirality, which are three critical prerequisites for achieving blue circularly polarized afterglow, has posed a formidable challenge. Herein, a straightforward approach is unveiled to attain blue circularly polarized afterglow materials by covalently self-confining isolated chiral chromophore within polymer matrix. The formation of robust hydrogen bonds within the polymer matrix confers a distinctly isolated and stabilized molecular state of chiral chromophores, endowing a blue emission band at 414 nm, lifetime of 3.0 s, and luminescent dissymmetry factor of ~ 10-2. Utilizing the synergistic afterglow and chirality energy transfer, full-color circularly polarized afterglow systems are endowed by doping colorful fluorescent molecules into designed blue polymers, empowering versatile applications. This work paves the way for the streamlined design of blue circularly polarized afterglow materials, expanding the horizons of circularly polarized afterglow materials into various domains.

Efficient metal free organic radical scintillators.

The development of high-performance metal-free organic X-ray scintillators (OXSTs), characterized by a synergistic combination of robust X-ray absorption, efficient exciton utilization, and short luminescence lifetimes, poses a considerable challenge. Here we present an effective strategy for achieving augmented X-ray scintillation through the utilization of halogenated open-shell organic radical scintillators. Our experimental results demonstrate that the synthesized scintillators exhibit strong X-ray absorption derived from halogen atoms, display efficacious X-ray stability, and theoretically achieve 100% exciton utilization efficiency with a short lifetime (∼18 ns) due to spin-allowed doublet transitions. The superior X-ray scintillation performance exhibited by these organic radicals is not only exploitable in X-ray radiography for contrast imaging of various objects but also applicable in a medical high-resolution micro-computer-tomography system for the clear visualization of fibrous veins within a bamboo stick. Our study substantiates the promise of organic radicals as prospective candidates for OXSTs, offering valuable insights and a roadmap for the development of advanced organic radical scintillators geared towards achieving high-quality X-ray radiography.

Constructing Organic Phosphorescent Scintillators with Enhanced Triplet Exciton Utilization Through Multi-Mode Radioluminescence for Efficient X-Ray Imaging.

The development of organic phosphorescent scintillators with high exciton utilization efficiency has attracted significant attention but remains a difficult challenge because of the inherent spin-forbidden feature of X-ray-induced triplet excitons. Herein, a design strategy is proposed to develop organic phosphorescent scintillators through thermally activated exciton release to convert stabilized spin-forbidden triplet excitons to spin-allowed singlet excitons, which enables singlet exciton-dominated multi-mode emission simultaneously from the lowest singlet, triplet, and stabilized triplet states. The resultant scintillators demonstrate a maximum photoluminescence efficiency of 65.8% and a minimum X-ray radiation detection limit of 110 nGy s-1; this allows efficient radiography imaging with a spatial resolution of ≈10.0 lp mm-1. This study advances the fundamental understanding of exciton dynamics under X-ray excitation, significantly broadening the practical use of phosphorescent materials for safety-critical industries and medical diagnostics.

Highly stable color-tunable organic long-persistent luminescence from a single-component exciplex copolymer for in vitro antibacterial.

Developing exciplex-based organic long-persistent luminescence (OLPL) materials with high stability is very important but remains a formidable challenge in a single-component system. Here, we report a facile strategy to achieve highly stable OLPL in an amorphous exciplex copolymer system via through-space charge transfer (TSCT). The copolymer composed of electron donor and acceptor units can not only exhibit effective TSCT for intra/intermolecular exciplex emission but also construct a rigid environment to isolate oxygen and suppress non-radiative decay, thereby enabling stable exciplex-based OLPL emission with color-tunable feature for more than 100 h under ambient conditions. These single-component OLPL copolymers demonstrate robust antibacterial activity against Escherichia coli under visible light irradiation. These results provide a solid example to exploit highly stable exciplex-based OLPL in polymers, shedding light on how the TSCT mechanism may potentially contribute to OLPL in a single-component molecular system and broadening the scope of OLPL applications.

Multicolor hyperafterglow from isolated fluorescence chromophores.

High-efficiency narrowband emission is always in the central role of organic optoelectronic display applications. However, the development of organic afterglow materials with sufficient color purity and high quantum efficiency for hyperafterglow is still great challenging due to the large structural relaxation and severe non-radiative decay of triplet excitons. Here we demonstrate a simple yet efficient strategy to achieve hyperafterglow emission through sensitizing and stabilizing isolated fluorescence chromophores by integrating multi-resonance fluorescence chromophores into afterglow host in a single-component copolymer. Bright multicolor hyperafterglow with maximum photoluminescent efficiencies of 88.9%, minimum full-width at half-maximums (FWHMs) of 38 nm and ultralong lifetimes of 1.64 s under ambient conditions are achieved. With this facilely designed polymer, a large-area hyperafterglow display panel was fabricated. By virtue of narrow emission band and high luminescent efficiency, the hyperafterglow presents a significant technological advance in developing highly efficient organic afterglow materials and extends the domain to new applications.

Achieving Balanced Electrical Performance of Host Material through Dual N-P═O Resonance Linkage for Efficient Electroluminescence.

Developing high-performance host materials is one of the biggest challenges for blue and white thermally activated delayed-fluorescence (TADF) organic light-emitting diode (OLED) technology due to the rigorous requirements of both efficient carrier flux ability and high triplet energy (ET) levels in static donor-acceptor molecules. Here, with the aid of a dual-resonance strategy, a host molecule showing dynamic adaption features in the acceptor-resonance-donor-resonance-acceptor (A-r-D-r-A) molecular configuration has been successfully developed through the implantation of two acceptors of diphenylphosphine oxide into electron-donating 5,10-dihydrophenazine with N-P═O resonance linkages. Owing to the dual enantiotropic N+═P-O- resonances, the designed A-r-D-r-A molecule exhibits an extraordinarily balanced charge flux transportation attribute at high ET (2.96 eV). Excitingly, blue and warm-white TADF OLEDs hosted by the A-r-D-r-A molecule exhibit outstanding external quantum efficiencies of 14.7 and 20.3%, respectively. Our studies not only broaden the scope of resonance molecules but also indicate that a resonance structure is an effective linkage to develop optoelectronic materials with dynamically adaptive properties.

On-demand modulating afterglow color of water-soluble polymers through phosphorescence FRET for multicolor security printing.

Developing full-color organic ultralong room temperature phosphorescence (OURTP) materials with continuously variable afterglow emission is of considerable practical importance in diverse optoelectronic applications but remains a formidable challenge. Here, we present an effective strategy for on-demand engineering of afterglow color in water-soluble polymeric systems via efficient phosphorescence Förster resonance energy transfer. Using a blue afterglow emitting water-soluble polymer as host and a series of fluorescent emitters with varied emissive colors as guests, afterglow emission is rationally modulated, conferring the full-color afterglow emission ranging from blue to red and even white with ultralong lifetimes up to 4.2 s and photoluminescence quantum yields of 36%.These water-soluble multicolor-emitting polymeric afterglow systems can function as OURTP security inks, and multilevel information encryption was successfully established by RGB-based multicolor security printing. These results present important guidance in developing high-performance afterglow polymers with on-demand color tuning ability for remarkable optoelectronic applications.

Single-component color-tunable circularly polarized organic afterglow through chiral clusterization.

Circularly polarized organic afterglow (CPOA) with both long-lived room-temperature phosphorescence (RTP) and circularly polarized luminescence (CPL) is currently attracting great interest, but the development of multicolor-tunable CPOA in a single-component material remains a formidable challenge. Here, we report an efficient strategy to achieve multicolor CPOA molecules through chiral clusterization by implanting chirality center into non-conjugated organic cluster. Owing to excitation-dependent emission of clusters, highly efficient and significantly tuned CPOA emissions from blue to yellowish-green with dissymmetry factor over 2.3 × 10-3 and lifetime up to 587 ms are observed under different excitation wavelengths. With the distinguished color-tunable CPOA, the multicolor CPL displays and visual RTP detection of ultraviolent light wavelength are successfully constructed. These results not only provide a new paradigm for realization of multicolor-tunable CPOA materials in single-component molecular systems, but also offer new opportunities for expanding the applicability of CPL and RTP materials for diversified applications.

Synthesis and characterization of two different azarubrenes.

The synthesis, properties and solid state X-ray single crystal structures of two new rubrene-derivatives, viz diazarubrene (4,4'-(6,12-diphenyltetracene-5,11-diyl)dipyridine) and tetraazarubrene (5,6,11,12-tetra(pyridin-4-yl)tetracene), are reported. Both the azarubrenes are more oxidatively stable than rubrene itself and show very similar optical properties but differ in their crystal packing from that of rubrene.

Fluorescent Organic Planar pn Heterojunction Light-Emitting Diodes with Simplified Structure, Extremely Low Driving Voltage, and High Efficiency.

Fluorescent organic light-emitting diodes capable of radiative utilization of both singlet and triplet excitons are achieved via a simple double-layer planar pn hetero-junction configuration without a conventional emission layer, leading to high external quantum efficiency above 10% and extremely low driving voltages close to the theoretical minima.

Polarity-Tunable Host Materials and Their Applications in Thermally Activated Delayed Fluorescence Organic Light-Emitting Diodes.

A series of polarity-tunable host materials were developed based on oligocarbazoles and diphenylphosphine oxide, and their polarities can be tuned through increasing distance of acceptor and donor units. Density functional theory calculations were employed, and photoluminescence spectra in different polar solvents were measured to illustrate different polarities of these host materials. As CZPO has relatively stronger polarity, electroluminescence (EL) spectrum of solution-processed device based on 6 wt % PXZDSO2:CZPO is 7 nm red-shifted relative to that of other host materials based devices. Besides, a comparable impressive external quantum efficiency (EQE) value of 18.7% is achieved for an evaporation-processed yellow device consisting of FCZBn, which is superior to that of the device based on CBP (4,4'-dicarbazolyl-1,1'-biphenyl) (17.0%), and its efficiency roll-off is also obviously reduced, giving an EQE value as high as 16.3% at the luminance of 1000 cd/m2. In addition, from CZPO to FCZBn as the polarities of host materials decrease, EL spectra of solution-processed devices based on DMAC-DPS emitter blue-shift constantly from 496 to 470 nm. The current work gives a constructive approach to control EL spectra of organic light-emitting diodes with a fixed thermally activated delayed fluorescence emitter by tuning the polarities of host materials.

"Rate-limited effect" of reverse intersystem crossing process: the key for tuning thermally activated delayed fluorescence lifetime and efficiency roll-off of organic light emitting diodes.

Issues concerning excited state lifetime (τTADF) tuning of thermally activated delayed fluorescence (TADF) materials are critical for organic light emitting diode (OLED) applications and other specific fields. For TADF-OLEDs, employing emitters with a short τTADF gives rise to suppressed singlet-triplet annihilation (STA) and triplet-triplet annihilation (TTA), leading to reduced efficiency roll-off at practical relevant brightness (100 and 1000 cd m-2 for display and illumination applications, respectively). Through molecular design, exciton dynamic process rate constants including fluorescence (kF), intersystem crossing (kISC), internal conversion (kIC) and reverse intersystem crossing (kRISC) are selectively altered, affording four representative TADF emitters. Based on lifetime and quantum yield measurements, kF, kISC, kIC and kRISC are calculated for four emitters and their interrelationship matches corrected time-dependent density functional theory simulation. Among them, even with a small kF, low photoluminescence quantum efficiency (Φ) and large kISC, molecules with a small singlet-triplet splitting energy (ΔEST) and lowest charge transfer triplet excited state (3CT) eventuate in shortening the τTADF. Herein, kRISC, which is inversely proportional to ΔEST, turns out to be the rate-limited factor in tuning the τTADF ("rate limited effect" of the RISC process). As revealed by flexible potential surface scanning, PyCN-ACR exhibited a moderate kF, reduced kIC and enlarged kRISC, resulting in a short τTADF and a moderate Φ with orange-red emission. OLEDs containing PyCN-ACR as the emitting guest achieved orange-red TADF-OLEDs with an emission peak at 590 nm and the best external quantum efficiencies (EQEs) of 12.4%/9.9%/5.1% at practical luminances of 100/1000/10 000 cd m-2.