Organic semiconductors can be designed and constructed in π‐stacked structures instead of the conventional π‐conjugated structures. Through‐space interaction (TSI) occurs in π‐stacked optoelectronic ...materials. Thus, unlike electronic coupling along the conjugated chain, the functional groups can stack closely to facilitate spatial electron communication. Using π‐stacked motifs, chemists and materials scientists can find new ways for constructing materials with aggregation‐induced emission (AIE), thermally activated delayed fluorescence (TADF), circularly polarized luminescence (CPL), and room‐temperature phosphorescence (RTP), as well as enhanced molecular conductance. Organic optoelectronic devices based on π‐stacked molecules have exhibited very promising performance, with some of them exceeding π‐conjugated analogues. Recently, reports on various organic π‐stacked structures have grown rapidly, prompting this review. Representative molecular scaffolds and newly developed π‐stacked systems could stimulate more attention on through‐space charge transfer the well‐known through‐bond charge transfer. Finally, the opportunities and challenges for utilizing and improving particular materials are discussed. The previous achievements and upcoming prospects may provide new insights into the theory, materials, and devices in the field of organic semiconductors.
Unlike traditional covalent bond‐connected conjugated molecules, π‐stacked small molecules have special advantages in organic semiconductors. This review mainly focuses on the research development of π‐stacked molecular systems and introduces the new characteristics brought by the special molecular configuration and its application in organic semiconductors.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
White‐light‐emissive organic micro/nanostructures hold exotic potential applications in full‐color displays, on‐chip wavelength‐division multiplexing, and backlights of portable display devices, but ...are rarely realized in organic core/shell heterostructures. Herein, through regulating the noncovalent interactions between organic semiconductor molecules, a hierarchical self‐assembly approach of horizontal epitaxial‐growth is demonstrated for the fine synthesis of organic core/mono‐shell microwires with multicolor emission (red–green, red–blue, and green–blue) and especially organic core/double‐shell microwires with radial red–green–blue (RGB) emission, whose components are dibenzog,pchrysene (DgpC)‐based charge‐transfer (CT) complexes. In fact, the desired lattice mismatching (≈2%) and the excellent structure compatibility of these CT complexes facilitate the epitaxial‐growth process for the facile synthesis of organic core/shell microwires. With the RGB‐emissive substructures, these core/double‐shell organic microwires are microscale white‐light sources (CIE 0.34, 0.36). Besides, the white‐emissive core/double‐shell microwires demonstrate the fascinating full‐spectrum light transportation from 400 to 700 nm. This work indeed opens up a novel avenue for the accurate construction of organic core/shell heterostructures, which provides an attractive platform for the organic integrated optoelectronics.
Through regulating the noncovalent interactions between organic semiconductor molecules (|ECT, DgpC‐TCNB = −18.35 kcal mol−1| > |ECT, DgpC‐TFP = −13.45 kcal mol−1| > |Eπ–π, DgpC = −6.81 kcal mol−1|), a hierarchical self‐assembly approach of horizontal epitaxial‐growth is demonstrated for the precise synthesis of organic core/double‐shell microwires with radial red–green–blue (RGB) substructures for miniaturized white‐light sources (CIE 0.34, 0.36).
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Multi‐layer π‐stacked emitters based on spatially confined donor/acceptor/donor (D/A/D) patterns have been developed to achieve high‐efficiency thermally activated delayed fluorescence (TADF). In ...this case, dual donor moieties and a single acceptor moiety are introduced to form two three‐dimensional (3D) emitters, DM‐BD1 and DM‐BD2, which rely on spatial charge transfer (CT). Owing to the enforced face‐to‐face D/A/D pattern, effective CT interactions are realized, which lead to high photoluminescence quantum yields (PLQYs) of 94.2 % and 92.8 % for the two molecules, respectively. The resulting emitters exhibit small singlet–triplet energy splitting (ΔEST) and fast reverse intersystem crossing (RISC) processes. Maximum external quantum efficiencies (EQEs) of 28.0 % and 26.6 % were realized for devices based on DM‐BD1 and DM‐BD2, respectively, which are higher than those of their D/A‐type analogues.
Multi‐Layer π‐stacked molecules are designed to realize efficient thermally activated delayed fluorescence. Spatially confined molecules with stereochemical structures are constructed in donor/acceptor/donor architectures with different conformations. Their organic light‐emitting diode (OLED) devices exhibit high external quantum efficiencies (EQEs) of 28.0 %/26.6 %, respectively.
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Harvesting the narrow bandgap excitons of charge‐transfer (CT) complexes for the achievement of near‐infrared (NIR) emission has attracted intensive attention for its fundamental importance and ...practical application. Herein, the triphenylene (TP)‐2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ) CT organic complex is designed and fabricated via the supramolecular self‐assembly process, which demonstrates the NIR emission with a maximum peak of 770 nm and a photoluminescence quantum yield (PLQY) of 5.4%. The segregated stacking mode of TP‐F4TCNQ CT complex based on the multiple types of intermolecular interaction has a low CT degree of 0.00103 and a small counter pitch angle of 40° between F4TCNQ and TP molecules, which breaks the forbidden electronic transitions of CT state, resulting in the effective NIR emission. Acting as the promising candidates for the active optical waveguide in the NIR region beyond 760 nm, the self‐assembled TP‐F4TCNQ single‐crystalline organic microwires display an ultralow optical‐loss coefficient of 0.060 dB µm−1. This work holds considerable insights for the exploration of novel NIR‐emissive organic materials via an universal “cocrystal engineering” strategy.
Through changing mixed stacking into segregated stacking mode, triphenylene (TP)‐2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ) charge‐transfer (CT) complex demonstrates a low CT degree and a small counter pitch angle between TP and F4TCNQ molecules, benefiting for breaking the forbidden electronic transitions of CT state for realizing the near‐infrared emission with a maximum peak of 770 nm and a photoluminescence quantum yield of 5.4%.
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A multiple resonance thermally activated delayed fluorescence (MR‐TADF) molecule with a fused, planar architecture tends to aggregate at high doping ratios, resulting in broad full width at half ...maximum (FWHM), redshifting electroluminescence peaks, and low device efficiency. Herein, we propose a mono‐substituted design strategy by introducing spiro‐9,9′‐bifluorene (SBF) units with different substituted sites into the MR‐TADF system for the first time. As a classic steric group, SBF can hinder interchromophore interactions, leading to high device efficiency (32.2–35.9 %) and narrow‐band emission (≈27 nm). Particularly, the shield‐like molecule, SF1BN, seldom exhibits a broadened FWHM as the doping ratio rises, which differs from the C3‐substituted isomer and unhindered parent emitter. These results manifest an effective method for constructing highly efficient MR‐TADF emitters through a spiro strategy and elucidate the feasibility for steric modulation of the spiro structure in π‐framework.
By incorporating a three‐dimensional spiro unit into multiple resonance thermally activated delayed fluorescence emitters, the device efficiency is increased to nearly 1.5 times that of the unhindered emitter. Notably, the linkage pattern with spatial interaction and hindrance can maintain the narrow FWHM and curb unfavorable redshifts at a high doping ratio.
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Charge-transfer (CT) complexes, formed by electron transfer from a donor to an acceptor, play a crucial role in organic semiconductors. Excited-state CT complexes, termed exciplexes, harness both ...singlet and triplet excitons for light emission, and are thus useful for organic light-emitting diodes (OLEDs). However, present exciplex emitters often suffer from low photoluminescence quantum efficiencies (PLQEs), due to limited control over the relative orientation, electronic coupling and non-radiative recombination channels of the donor and acceptor subunits. Here, we use a rigid linker to control the spacing and relative orientation of the donor and acceptor subunits, as demonstrated with a series of intramolecular exciplex emitters based on 10-phenyl-9,10-dihydroacridine and 2,4,6-triphenyl-1,3,5-triazine. Sky-blue OLEDs employing one of these emitters achieve an external quantum efficiency (EQE) of 27.4% at 67 cd m
with only minor efficiency roll-off (EQE = 24.4%) at a higher luminous intensity of 1,000 cd m
. As a control experiment, devices using chemically and structurally related but less rigid emitters reach substantially lower EQEs. These design rules are transferrable to other donor/acceptor combinations, which will allow further tuning of emission colour and other key optoelectronic properties.
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FZAB, GEOZS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Three emissive bridged-triphenylamine derivatives are designed and synthesized by incorporating carbon (DQAO), oxygen (OQAO), and sulfur (SQAO) atoms with two carbonyl groups. The fully bridged ...geometry and unique frontier molecular orbital distribution reveal its potential as narrowband thermally activated delayed fluorescence emitters. DQAO-, OQAO-, and SQAO-based organic light-emitting diodes exhibit the maximum external quantum efficiency (EQEmax) of 15.2%, 20.3%, and 17.8% for blue, green, and yellow, respectively.
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Metal halide perovskite semiconductors have demonstrated remarkable potentials in solution‐processed blue light‐emitting diodes (LEDs). However, the unsatisfied efficiency and spectral stability ...responsible for trap‐mediated non‐radiative losses and halide phase segregation remain the primary unsolved challenges for blue perovskite LEDs. In this study, it is reported that a fluorene‐based π‐conjugated cationic polymer can be blended with the perovskite semiconductor to control film formation and optoelectronic properties. As a result, sky‐blue and true‐blue perovskite LEDs with Commission Internationale de l'Eclairage coordinates of (0.08, 0.22) and (0.12, 0.13) at the record external quantum efficiencies of 11.2% and 8.0% were achieved. In addition, the mixed halide perovskites with the conjugated cationic polymer exhibit excellent spectral stability under external bias. This result illustrates that π‐conjugated cationic polymers have a great potential to realize efficient blue mixed‐halide perovskite LEDs with stable electroluminescence.
A fluorene‐based π‐conjugated cationic polymer as a multifunctional passivator to suppress non‐radiative processes, improve charge transport properties, and inhibit ion migration for blue mixed‐halide perovskite semiconductors, is reported. As a result, efficient and spectrally stable blue perovskite light‐emitting diodes with emission wavelengths from 485 to 458 nm are achieved.
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In the field of phosphorescent organic light-emitting diodes (PhOLEDs), designing high-efficiency universal host materials for red, green and blue (RGB) phosphors has been quite a challenge. To date, ...most of the high-efficiency universal hosts reported incorporate heteroatoms, which have a crucial role in the device performance. However, the introduction of different kinds of heterocycles increases the design complexity and cost of the target material and also creates potential instability in the device performance. In this work, we show that pure aromatic hydrocarbon hosts designed with the 9,9′-spirobifluorene scaffold are high-efficiency and versatile hosts for PhOLEDs. With external quantum efficiencies of 27.3%, 26.0% and 27.1% for RGB PhOLEDs respectively, this work not only reports the first examples of high-efficiency pure hydrocarbon materials used as hosts in RGB PhOLEDs but also the highest performance reported to date for a universal host (including heteroatom-based hosts). This work shows that the PHC design strategy is promising for the future development of the OLED industry as a high-performance and low-cost option.
In this work, we propose pure hydrocarbon materials as universal hosts for high-efficiency red, green and blue phosphorescent organic light-emitting diodes.
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Understanding the movement of polycyclic aromatic hydrocarbons (PAHs) from emission sources to sediments is important for achieving long-term pollution control of PAHs in sediments. In this study, by ...exploring the correlation of individual PAHs concentrations (CPAHs) in Taihu Lake sediments reported in the past twenty years with their annual emissions (EPAHs) in the lake region, it was observed that mean concentrations of PAHs with low logKow (i.e., logKow≤4.00) in Taihu Lake sediments were correlated best with their emissions without lagging between the sediment sampling time and the PAHs emitting time. However, for PAHs with middle logKow (i.e., 4.00<logKow≤4.57) or high logKow (i.e., logKow>4.57), their mean concentrations in sediments were correlated best with the emissions of PAHs emitted 1 or 2 years before the sediment sampling time. The longer lagging time of PAHs with middle or high logKow from emission sources to lake sediments could be attributed to their retardation in soils and river sediments around the lake. Moreover, the retardation in soils and river sediments is dependent on PAHs logKow and degradation half-life, indicating the dependence of PAHs concentration in sediments on their environmental behaviors, including sorption and degradation. Kow dependent movement and the time lagging observed in Taihu Lake for PAHs from emission sources to sediments could be valuable for developing measures to control PAHs, especially for congeners with high logKow.
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•Time lagging for PAHs from emission to sediments observed.•Lagging of PAHs attributed to retarding on soils and river sediments.•PAHs retarding on soils and river sediments is dependent on their logKow.•Movement hysteresis of PAHs is valuable for controlling PAHs into sediments.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
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