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Low-cost molecular emitters that merge circularly polarized luminescence (CPL) and thermally activated delayed fluorescence (TADF) properties are attractive for many high-tech applications. However, the design of such emitters remains a difficult task. To address this challenge, here, we propose a simple and efficient strategy, demonstrated by the design of pseudochiral-at-metal complexes [Cu(L*)DPEPhos]PF6 bearing a (+)/(-)-menthol-derived 1,10-phenanthroline ligand (L*). These complexes exhibit a yellow CP-TADF with a record-high quantum yield (close to 100%) and high dissymmetry factor (|glum| ~ 1×10-2). Remarkably, the above compounds also show a negative thermal-quenching (NTQ) of luminescence in the 300-77 K range. Exploiting the designed Cu(I) emitters, we fabricated efficient CP-TADF OLEDs displaying mirror-imaged CPL bands with high |gEL| factors of 1.5×10-2 and the maximum EQE of 6.15%. Equally important, using the (+)-[Cu(L*)DPEPhos]PF6 complex, we have discovered that an external magnetic field noticeably suppresses CP-TADF of Cu(I) emitters. These findings are an important contribution to the CPL phenomenon and provide access to highly efficient, low-cost and robust CP-TADF emitters.
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This review comprehensively addresses the developments and applications of polymer materials in optoelectronics. Especially, this review introduces how the materials absorb, emit, and transfer charges, including the exciton-vibrational coupling, nonradiative and radiative processes, Förster Resonance Energy Transfer (FRET), and energy dynamics. Furthermore, it outlines charge trapping and recombination in the materials and draws the corresponding practical implications. The following section focuses on the practical application of organic materials in optoelectronics devices and highlights the detailed structure, operational principle, and performance metrics of organic photovoltaic cells (OPVs), organic light-emitting diodes (OLEDs), organic photodetectors, and organic transistors in detail. Finally, this study underscores the transformative impact of organic materials on the evolution of optoelectronics, providing a comprehensive understanding of their properties, mechanisms, and diverse applications that contribute to advancing innovative technologies in the field.
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Fourteen substituted diketopyrrolopyrrole (DPP) molecules in a donor (D)-acceptor (DPP)-donor (D) arrangement were designed. We employed density functional theory, time-dependent DFT, DFT-MRCI and the ab initio wave function second-order algebraic diagrammatic construction (ADC(2)) methods to investigate theoretically these systems. The examined aromatic substituents have one, two, or three hetero- and non-hetero rings. We comprehensively investigated their optical, electronic, and charge transport properties to evaluate potential applications in organic electronic devices. We found that the donor substituents based on one, two, or three aromatic rings bonded to the DPP core can improve the efficiency of an organic solar cell by fine-tuning the highest occupied molecular orbital/lowest unoccupied molecular orbital levels to match acceptors in typical bulk heterojunctions acceptors. Several properties of interest for organic photovoltaic devices were computed. We show that the investigated molecules are promising for applications as donor materials when combined with typical acceptors in bulk heterojunctions because they have appreciable energy conversion efficiencies resulting from their low ionization potentials and high electron affinities. This scenario allows a more effective charge separation and reduces the recombination rates. A comprehensive charge transfer analysis shows that D-A (DDP)-D systems have significant intramolecular charge transfer, further confirming their promise as candidates for donor materials in solar cells. The significant photophysical properties of DPP derivatives, including the high fluorescence emission, also allow these materials to be used in organic light-emitting diodes.
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Multi-resonance (MR) type emitters have emerged as highly promising candidates for high-resolution organic light-emitting diodes (OLEDs). However, thermally activated delayed fluorescence (TADF) emissions with simultaneous short excited state lifetimes and ultrapure blue color (a CIEy close to 0.046 and an emission peak > 440 nm) have rarely been obtained for MR emitters. Herein, we report a design of dual gold-coordinated MR molecules to achieve efficient and short-lived ultrapure blue TADF emission. The dinuclear Au(I) complex, namely iPrAuBN, shows a narrowband deep-blue emission with a peak maximum of 448 nm and a full width at half maximum (FWHM) of 29 nm in doped film. The coordination with two Au atoms significantly shortens the delayed fluorescence lifetime to 7.8 µs in comparing with 60.6 µs for the organic analogue. Solution-processed OLED doped with iPrAuBN demonstrates an ultrapure blue electroluminescence with a peak maximum of 442 nm, a FWHM of 19 nm, Commission International de l'Éclairage (CIE) coordinates of (0.154, 0.036), and a maximum external quantum efficiency of 14.8%.
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The analysis of the shift in photoluminescence emission for a blend of polyvinylcarbazole and acrylonitrile derivative compounds is reported. The small-molecule compounds have different functional groups, phenyl, pyridine, or methyl phenyl, attached to an acrylonitrile group. According to the functional group, the blue emission for pure dye shifts to green or yellowish in the blend film. Several PVK:dye ratios from 0:100 to 20:80 were used for film deposition. The film morphology was analyzed by atomic force microscopy; for low dye content, homogeneous films were achieved. However, aggregates of several micrometers are formed on the surface of films with higher dye concentrations. The shift in emission occurs only with PVK, and for a non-conjugated matrix such as polystyrene, the emission remains unchanged. The interaction of dyes with PVK leading to change in emission was also achieved by grinding dye and polymer. Results showed that shifts in emission could come from exciplex formation along with changes in dye intermolecular interactions. The blend films were highly transparent in the visible spectra due to the absorption in the UV region for dye and matrix. The films with ratio PVK: dye ratio 80:20 was used as active layer in OLEDs.
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Six novel red photoluminescent Eu3+ complexes with 3-formyl chromone as the primary sensitizer (L) were synthesized using the solution precipitation method. These complexes are [Eu(L3).X] where X is 2H2O (C1), phen (C2), neo (C3), bipy (C4), dmph (C5), and biquno (C6). These complexes were characterized by elemental analysis, EDAX analysis, SEM, FT-IR, thermo-gravimetric analysis (TGA/DTA) and photoluminescence spectra. The transition rates, quantum efficiency, and J-O intensity parameters were calculated using emission data and luminescence decay time (τ). Complexes exhibit a strong emission peak (5D0 â 7F2) of the Eu3+ ion in their luminescence emission spectra in solid and solution states, making them an effective emitter of the red color in OLEDs. The branching ratio of these complexes ranges from 80.67-82.92 in solid and 50.53-62.65 in solution state; CIE color coordinate of complexes falls in the red region. The color purity ranges [CP(%)] values for solid 95.26-97.27% and for solution ranges 85.11-93.43%. Correlated color temperature (CCT) of the complexes (C1-C6) ranged from 2710 to 3049 K in the solid state and 1775 to 2450 K in the solution state. These complexes are promising red emitters in OLEDs, semiconductors, and leasing devices.
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In the last past twenty years, research on luminescent platinum (II) complexes has been intensively developed for useful application such as organic light emitting diodes (OLEDs). More recently, new photoluminescent complexes based on diazine ligands (pyrimidine, pyrazine, pyridazine, quinazoline and quinoxaline) have been developed in this context. This review will summarize the photophysical properties of most of the phosphorescent diazine Pt(II) complexes described in the literature and compare the results to pyridine analogues whenever possible. Based on the emission color, and the photoluminescence quantum yield (PLQY) values, the relationship between structure modification, and photophysical properties are highlighted. Tuning of emission color, quantum yields in solution and solid state and, for some complexes, aggregation induced emission (AIE) or thermally activated delayed fluorescence (TADF) properties are described. When emitting OLEDs have been built from diazine Pt(II) complexes, the external quantum efficiency (EQE) values and luminance for different emission wavelengths and in some cases, chromaticity coordinates obtained from devices, are given. Finally, this review highlights the growing interest in studies of new luminescent diazine Pt(II) complexes for OLED applications.
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Cutaneous leishmaniasis (CL) is a neglected disease caused by Leishmania parasites. The oral drug miltefosine is effective, but there is a growing problem of drug resistance, which has led to increasing treatment failure rates and relapse of infections. Photodynamic therapy (PDT) combines a light source and a photoactive drug to promote cell death by oxidative stress. Although PDT is effective against several pathogens, its use against drug-resistant Leishmania parasites remains unexplored. Herein, we investigated the potential of organic light-emitting diodes (OLEDs) as wearable light sources, which would enable at-home use or ambulatory treatment of CL. We also assessed its impact on combating miltefosine resistance in Leishmania amazonensis-induced CL in mice. The in vitro activity of OLEDs combined with 1,9-dimethyl-methylene blue (DMMB) (OLED-PDT) was evaluated against wild-type and miltefosine-resistant L. amazonensis strains in promastigote (EC50 = 0.034 µM for both strains) and amastigote forms (EC50 = 0.052 µM and 0.077 µM, respectively). Cytotoxicity in macrophages and fibroblasts was also evaluated. In vivo, we investigated the potential of OLED-PDT in combination with miltefosine using different protocols. Our results demonstrate that OLED-PDT is effective in killing both strains of L. amazonensis by increasing reactive oxygen species and stimulating nitric oxide production. Moreover, OLED-PDT showed great antileishmanial activity in vivo, allowing the reduction of miltefosine dose by half in infected mice using a light dose of 7.8â¯J/cm2 and 15 µM DMMB concentration. In conclusion, OLED-PDT emerges as a new avenue for at-home care and allows a combination therapy to overcome drug resistance in cutaneous leishmaniasis.
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Resistência a Medicamentos , Leishmaniose Cutânea , Camundongos Endogâmicos BALB C , Fosforilcolina , Fotoquimioterapia , Animais , Fotoquimioterapia/métodos , Leishmaniose Cutânea/tratamento farmacológico , Leishmaniose Cutânea/parasitologia , Fosforilcolina/análogos & derivados , Fosforilcolina/farmacologia , Fosforilcolina/uso terapêutico , Camundongos , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/uso terapêutico , Antiprotozoários/farmacologia , Antiprotozoários/uso terapêutico , Feminino , Leishmania/efeitos dos fármacos , Macrófagos/parasitologia , Macrófagos/efeitos dos fármacos , Macrófagos/metabolismoRESUMO
Organic light-emitting diodes (OLEDs) that are able to emit high levels of circularly polarized (CP) light hold significant promise in numerous future technologies. Such devices require chiral emissive materials to enable CP electroluminescence. However, the vast majority of current OLED emitter classes, including the state-of-the-art triplet-harvesting thermally activated delayed fluorescence (TADF) materials, produce very low levels of CP electroluminescence. Here a host-guest strategy that allows for energy transfer between a chiral polymer host and a representative chiral TADF emitter is showcased. Such a mechanism results in a large amplification of the circular polarization of the emitter. As such, this study presents a promising avenue to further boost the performance of circularly polarized organic light-emitting diode devices, enabling their further development and eventual commercialization.
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We introduce three newly designed thermally cross-linkable hole transport copolymers (PIF-TPD, PIF-F2PCz, and PIF-TPAPCz) for improving the performance of solution-processed organic light-emitting diodes (s-OLEDs). These copolymers, designed through a strategic molecular approach with benzocyclobutene (BCB) and styrene-based cross-linking monomers, show high solvent resistance at a low cross-linking temperature (150 °C). Furthermore, these conjugated copolymers based on planar indenofluorene with three different hole transport (HT) units, exhibit outstanding charge carrier mobility (1.61 × 10-2 cm2 V-1s-1), demonstrated by comparing hole reorganization energy and electronic coupling strength of HT units. Despite these copolymers showing the overall vertical orientation in the horizontal dipole moment measurement results, we demonstrated that the HT units can exhibit the preferred orientation, contributing to high hole transport properties. As a result, they perform exceptionally well as hole transport layers in green phosphorescent s-OLEDs, achieving a maximum external quantum efficiency of 15.3% and a maximum current efficiency of 53.9 cd A-1 with a small efficiency roll-off despite their relatively low triplet energy levels. These results are comparable to vacuum-deposited OLEDs, highlighting the potential of these copolymers in advancing OLED technology for display panels and lighting applications.
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Despite multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitters with small full-width at half maximum are attractive for wide color-gamut display and eye-protection lighting applications, their inefficient reverse intersystem crossing (RISC) process and long exciton lifetime induce serious efficiency roll-off, which significantly limits their development. Herein, a novel device concept of building highly efficient tricomponent exciplex with multiple RISC channels is proposed to realize reduced exciton quenching and enhanced upconversion of nonradiative triplet excitons, and subsequently used as a host for high-performance MR-TADF organic light-emitting diodes (OLEDs). Compared with traditional binary exciplex, the tricomponent exciplex exhibits obviously improved photoluminescence quantum yield, emitting dipole orientation and RISC rate constant, and a record-breaking external quantum efficiency (EQE) of 30.4% is achieved for tricomponent exciplex p-PhBCzPh: PO-T2T: DspiroAc-TRZ (50: 20: 30) based OLED. Remarkably, maximum EQEs of 36.2% and 40.3% and ultralow efficiency roll-off with EQEs of 26.1% and 30.0% at 1000 cd m-2 are respectively achieved for its sky-blue and pure-green MR-TADF doped OLEDs. Additionally, the blue emission unit hosted by tricomponent exciplex is combined with an orange-red TADF emission unit to achieve a double-emission-layer blue-hazard-free warm white OLED with an EQEmax of 30.3% and stable electroluminescence spectra over a wide brightness range.
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9,9-Dimethyl-9,10-dihydroacridine (DMAC) is one of the most widely used electron donor for constructing high-performance thermally activated delayed fluorescence (TADF) emitters. However, DMAC-based emitters often suffer from the imperfect color purity, particularly in blue emitters, due to its strong electron-donating capability. To modulate donor strength, 2,7-F-Ph-DMAC and 2,7-CF3-Ph-DMAC were designed by introducing the electron-withdrawing 2-fluorophenyl and 2-(trifluoromethyl)phenyl at the 2,7-positions of DMAC. These donors were used, in combination with 2,4,6-triphenyl-1,3,5-triazine (TRZ) acceptor, to develop novel TADF emitters 2,7-F-Ph-DMAC-TRZ and 2,7-CF3-Ph-DMAC-TRZ. Compared to the F- or CF3-free reference emitter, both two emitters showed hypsochromic effect in fluorescence and comparable photoluminescence quantum yields without sacrificing the reverse intersystem crossing rate constants. In particular, 2,7-CF3-Ph-DMAC-TRZ based OLED exhibited a blue shift by up to 39â nm and significantly improved Commission International de l'Éclairage (CIE) coordinates from (0.36, 0.55) to (0.22, 0.41), while the external quantum efficiency kept stable at about 22.5 %. This donor engineering strategy should be valid for improving the color purity of large amount of acridine based TADF emitters. It can be predicted that pure blue TADF emitters should be feasible if these F- or CF3-modifed acridine donors are combined with other weaker electron acceptors.
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Deep-blue multi-resonance (MR) emitters with stable and narrow full-width-at-half-maximum (FWHM) are of great importance for widening the color gamut of organic light-emitting diodes (OLEDs). However, most planar MR emitters are vulnerable to intermolecular interactions from both the host and guest, causing spectral broadening and exciton quenching in thin films. Their emission in the solid state is environmentally sensitive, and the color purity is often inferior to that in solutions. Herein, a molecular design strategy is presented that simultaneously narrows the FWHM and suppresses intermolecular interactions by combining intramolecular locking and peripheral shielding within a carbonyl/nitrogen-based MR core. Intramolecularly locking carbonyl/nitrogen-based bears narrower emission of 2,10-dimethyl-12,12-diphenyl-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine-4,8(12H)-dione in solution and further with peripheral-shielding groups, deep-blue emitter (12,12-diphenyl-2,10-bis(9-phenyl-9H-fluoren-9-yl)-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine-4,8(12H)-dione, DPQAO-F) exhibits ultra-pure emission with narrow FWHM (c.a., 24 nm) with minimal variations (∆FWHM ≤ 3 nm) from solution to thin films over a wide doping range. An OLED based on DPQAO-F presents a maximum external quantum efficiency (EQEmax) of 19.9% and color index of (0.134, 0.118). Furthermore, the hyper-device of DPQAO-F exhibits a record-high EQEmax of 32.7% in the deep-blue region, representing the first example of carbonyl/nitrogen-based OLED that can concurrently achieve narrow bandwidth in the deep-blue region and a high electroluminescent efficiency surpassing 30%.
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The feature of abundant and environmentally friendly heavy atoms (HAs) like bromine to accelerate spin-forbidden transitions in organic molecules has been known for years. In combination with the easiness of incorporation, bromine derivatives of organic emitters showing thermally activated delayed fluorescence (TADF) emerge as a cheap and efficient solution for the slow reverse intersystem crossing (rISC) problem in such emitters and strong efficiency roll-off of all-organic light-emitting diodes (OLEDs). Here, we present a comprehensive photophysical study of a tri-PXZ-TRZ emitter reported previously and its hexabromo derivative showing a remarkable enhancement of rISC of up to 9 times and a short lifetime of delayed fluorescence of 2 µs. Analysis of the key molecular vibrations and TADF mechanism indicates almost compete blockage of the spin-flip transition between the charge-transfer states of different multiplicity 3CT â 1CT. In such a case, rISC as well as its enhancement by the HA is realized via the 3LE â 1CT transition, where 3LE is the triplet state localized on the same brominated phenoxazine donor involved in the formation of the 1CT state. Interestingly, the spin-orbit coupling (SOC) with two other 3LE states is negligible because they are localized on different donors and not involved in 1CT. We consider this as an example of an additional "localization" criterion that completes the well-known El Sayed rule on the different nature of states for nonzero SOC. The applicative potential of such a hexabromo emitter is tested in a "hyperfluorescent" system containing a red fluorescent dopant (tetraphenyldibenzoperiflanthene, DBP) as an acceptor of Förster resonance energy transfer, affording a narrow-band red-emitting system, with most of the emission in the submicrosecond domain. In fact, the fabricated red OLED devices show remarkable improvement of efficiency roll-off from 2-4 times depending on the luminance, mostly because of the increase of the rISC constant rate and the decrease of the overall delayed fluorescence lifetime thanks to the HA effect.
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Three new neutral and ionic phosphorescent iridium(III) complexes were successfully prepared using 1-(6-methoxynaphthalen-2-yl)isoquinoline as the main ligand, while the auxiliary ligand was 2-(2-1H-imidazolyl)pyridine. Three complexes (Ir1, Ir2, Ir3) showed red emission, peaking at 610, 609, and 615 nm, respectively, and they exhibited good solubility and excellent photophysical properties in different solvents, which is suitable to prepare organic light-emitting diodes (OLEDs) by solution method. Among the three OLEDs prepared by iridium(III) complexes using the solution method, the device based on Ir2 possessed better electroluminescent properties, and its maximum brightness, current efficiency (CE), power efficiency (PE), and the maximum external quantum efficiency (EQE) were 507.2 cd m-2 , 0.14 cd A-1 , 0.06 lm W-1 , and 0.14%. respectively, proving that the three complexes have a certain of potential for OLEDs applications and are expected to expand the applications of iridium(III) complexes for OLEDs.
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Irídio , Ligantes , Íons , Solubilidade , SolventesRESUMO
Up to now, highly efficient narrowband thermally activated delayed fluorescence (TADF) molecules constructed by oxygen-bridged boron with an enhancing multiple resonance (MR) effect have been in urgent demand for solid-state lighting and full-color displays. In this work, a novel MR-TADF molecule, BNBO, constructed by the oxygen-bridged boron unit and boron-nitrogen core skeleton as an electron-donating moiety, is successfully designed and synthesized via a facile one-step synthesis. Based on BNBO as an efficient green emitter, the organic light-emitting diode (OLED) shows a sharp emission peak of 508 nm with a full-width at half-maximum (FWHM) of 36 nm and realizes quite high peak efficiency values, including an external quantum efficiency (EQEmax) of 24.3% and a power efficiency (PEmax) of 62.3 lm/W. BNBO possesses the intramolecular charge transfer (ICT) property of donor-acceptor (D-A) materials and multiple resonance characteristics, which provide a simple strategy for narrowband oxygen-boron materials.
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Third-generation organic light-emitting diodes (OLEDs) based on metal-free thermally activated delayed fluorescent (TADF) materials have sparked tremendous interest in the last decade due to their nearly 100% exciton utilization efficiency, which can address the low-efficiency issue of the first-generation fluorescent emitters and the high-cost issue of the second-generation organometallic phosphorescent emitters. Construction of efficient and stable TADF-OLEDs requires utilizing TADF materials with a narrow singlet-triplet energy gap (ΔEST), high photoluminescence quantum yield (PLQY) and short TADF lifetime. A small ΔEST is necessary for an efficient reverse intersystem crossing (RISC) process, which can be achieved through the effective spatial separation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). TADF emitters have been generally designed as intramolecular charge transfer (ICT) molecules with highly twisted donor-acceptor (D-A) molecular architectures. A wide variety of combinations of electron donors and acceptors have been explored. In this review, we shall focus on recent progress in organic TADF molecules incorporating strong electron-donor phenoxazine moiety and their application as emitting layer (EML) in OLEDs.
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Corantes , OxazinasRESUMO
Three novel conjugated molecules have been synthesized: 2-(fluoranthen-3-yliminomethyl)-3,4-ethylenedioxythio-phene (EIF), 2-(fluoranthen-3-yliminomethyl) thiophene (TIF), and 2-(fluoranthen-3-yliminomethyl) fluorene (FIF). Optical properties were obtained from electronic absorption and emission spectra in DMSO solution. The solvatochromic properties of the molecules have been studied in different solvents. Electrochemical properties were studied by cyclic voltammetry in a Bu4NBF4 (0.1â M)/MeCN organic solution. As part of investigations to explain the nature of electronic transition process, we have performed geometry optimization of both the ground and the vertical excitation states, using the DFT B3LYP/6-311G (d, p) and TD-DFT (CPCM)/B3LYP/6-311G (d, p) approaches, respectively. Theoretical calculations closely match the experimental findings. Results show that EIF, TIF and FIF are potential candidates to be used as electron transport layer in Organic Light-Emitting Diodes (OLEDs).
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The use of conducting polymers in devices makes them desirable due to their allowance for the fabrication of flexible, lightweight, and potentially inexpensive devices. This review explores the synthetic strategies and characterizations of 3,6-substituted carbazole-based polymers, emphasizing the influence of these modifications on their electronic structure and absorption properties. Polymers containing carbazole substituents are widely studied due to their unique optical and electronic properties, high electron-donating ability, and photoconductivity. The structural adaptability of the carbazole with the 3,6-substitution makes it as an outstanding candidate for their integration into polymers and also possesses improved stability and triplet energy. The role of intramolecular charge transfer (ICT) was highlighted by donor-acceptor architectures with tailoring energy levels to extract their advantageous physicochemical characteristics and optimized performances. Collectively, this comprehensive review delves into the burgeoning field of 3,6-substituted carbazole-based polymers and their crucial role in advancing optoelectronic applications. By amalgamating materials design, synthetic strategies, and application-driven insights, the review serves as a valuable resource for researchers to understand the structure-property relationships and foster innovative solutions for next-generation opto-electronic applications.
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A novel class of o-carboranyl luminophores, 2CB-BuDABNA (1) and 3CB-BuDABNA (2) is reported, in which o-carborane moieties are incorporated at the periphery of the B,N-doped multi-resonance thermally activated delayed fluorescence (MR-TADF) core. Both compounds maintain the inherent local emission characteristics of their MR-emitting core, exhibiting intense MR-TADF with high photoluminescence quantum yields in toluene and rigid states. In contrast, the presence of the dark lowest-energy charge transfer state, induced by cage rotation in THF, is suggested to be responsible for emission quenching in a polar solvent. Despite the different arrangement of the cage on the DABNA core, both 1 and 2 show red-shifted emissions compared to the parent compound BuDABNA (3). By utilizing 1 as the emitter, high-efficiency blue organic light-emitting diodes (OLEDs) are achieved with a remarkable maximum external quantum efficiency of 25%, representing the highest reported efficiency for OLEDs employing an o-carboranyl luminophore as the emitter.