Bicarbazole-Benzophenone Based Twisted Donor-Acceptor Derivatives as Potential Blue TADF Emitters for OLEDs.

Over the past few decades, organic light-emitting diodes (OLEDs) find applications in smartphones, televisions, and the automotive sector. However, this technology is still not perfect, and its application for lighting purposes has been slow. For further development of the OLEDs, we designed twisted donor-acceptor-type electroactive bipolar derivatives using benzophenone and bicarbazole as building blocks. Derivatives were synthesized through the reaction of 4-fluorobenzophenone with various mono-alkylated 3,3'-bicarbazoles. We have provided a comprehensive structural characterization of these compounds. The new materials are amorphous and exhibit suitable glass transition temperatures ranging from 57 to 102 °C. They also demonstrate high thermal stability, with decomposition temperatures reaching 400 °C. The developed compounds exhibit elevated photoluminescence quantum yields (PLQY) of up to 75.5% and favourable HOMO-LUMO levels, along with suitable triplet-singlet state energy values. Due to their good solubility and suitable film-forming properties, all the compounds were evaluated as blue TADF emitters dispersed in commercial 4,4'-bis(N-carbazolyl)-1,10-biphenyl (CBP) host material and used for the formation of emissive layer of organic light-emitting diodes (OLEDs) in concentration-dependent experiments. Out of these experiments, the OLED with 15 wt% of the emitting derivative 4-(9'-{2-ethylhexyl}-[3,3']-bicarbazol-9-yl)benzophenone exhibited superior performance. It attained a maximum brightness of 3581 cd/m2, a current efficacy of 5.7 cd/A, a power efficacy of 4.1 lm/W, and an external quantum efficacy of 2.7%.

Sterically Crowded Donor-Rich Imidazole Systems as Hole Transport Materials for Solution-Processed OLEDs.

Imidazole, being an interesting dinitrogenic five-membered heterocyclic core, has been widely explored during the last several decades for developing various fascinating materials. Among the different domains where imidazole-based materials find wide applications, the area of optoelectronics has seen an overwhelming growth of functional imidazole derivatives developed through remarkable design and synthesis strategies. The present work reports a design approach for integrating bulky donor units at the four terminals of an imidazole core, leading to the development of sterically populated imidazole-based molecular platforms with interesting structural features. Rationally chosen starting substrates led to the incorporation of a bulky donor at the four terminals of the imidazole core. In addition, homo- and cofunctional molecular systems were synthesized through a suitable combination of initial ingredients. Our approach was extended to develop a series of four molecular systems, i.e., Cz3PhI, Cz4I, Cz3PzI, and TPA3CzI, containing carbazole, phenothiazine, and triphenylamine as known efficient donors at the periphery. Given their interesting structural features, three sterically crowded molecules (Cz4I, Cz3PzI, and TPA3CzI) were screened by using DFT and TD-DFT calculations to investigate their potential as hole transport materials (HTMs) for optoelectronic devices. The theoretical studies on several aspects including hole reorganization and exciton binding energies, ionization potential, etc., revealed their potential as possible candidates for the hole transport layer of OLEDs. Single-crystal analysis of Cz3PhI and Cz3PzI established interesting structural features including twisted geometries, which may help attain high triplet energy. Finally, the importance of theoretical predictions was established by fabricating two solution-process green phosphorescent OLED devices using TPA3CzI and Cz3PzI as HTMs. The fabricated devices exhibited good EQE/PE and CE of ∼15%/56 lm/W/58 cd/A and ∼13%/47 lm/W/50 cd/A, respectively, at 100 cd/m2.

Harnessing HfO2 Nanoparticles for Wearable Tumor Monitoring and Sonodynamic Therapy in Advancing Cancer Care.

Addressing the critical requirement for real-time monitoring of tumor progression in cancer care, this study introduces an innovative wearable platform. This platform employs a thermoplastic polyurethane (TPU) film embedded with hafnium oxide nanoparticles (HfO2 NPs) to facilitate dynamic tracking of tumor growth and regression in real time. Significantly, the synthesized HfO2 NPs exhibit promising characteristics as effective sonosensitizers, holding the potential to efficiently eliminate cancer cells through ultrasound irradiation. The TPU-HfO2 film, acting as a dielectric elastomer (DE) strain sensor, undergoes proportional deformation in response to changes in the tumor volume, thereby influencing its electrical impedance. This distinctive behavior empowers the DE strain sensor to continuously and accurately monitor alterations in tumor volume, determining the optimal timing for initiating HfO2 NP treatment, optimizing dosages, and assessing treatment effectiveness. Seamless integration with a wireless system allows instant transmission of detected electrical impedances to a smartphone for real-time data processing and visualization, enabling immediate patient monitoring and timely intervention by remote medical staff. By combining the dynamic tumor monitoring capabilities of the TPU-HfO2 film with the sonosensitizer potential of HfO2 NPs, this approach propels cancer care into the realm of telemedicine, representing a significant advancement in patient treatment.

Modifications of Pyridine-3,5-dicarbonitrile Acceptor for Highly Efficient Green-to-Red Organic Light-Emitting Diodes.

The strategy of acceptor modification is a powerful technique for tuning the emission color of thermally activated delayed fluorescence (TADF) emitters. In this study, we have successfully designed and synthesized three TADF emitters with donor-acceptor (D-A) structures using a 4-(diphenylamino)-2,6-dimethylphenyl (TPAm) donor and various pyridine-3,5-dicarbonitrile (PC) acceptor units. As a result, three compounds named TPAmbPPC, TPAm2NPC, and TPAmCPPC exhibited greenish-yellow to orange-red emissions with high photoluminescent quantum yields (76-100%) in thin films. Remarkably, a greenish-yellow device based on TPAmbPPC and TPAm2NPC showed a high maximum external quantum efficiency (EQEmax) of 39.1 and 39.0%, respectively. Furthermore, benefiting from the suitable steric hindrance between the acceptor and donor, the nondoped organic light-emitting diodes (OLEDs) based on TPAmbPPC demonstrated an exceptional EQEmax of 21.6%, indicating its promising potential as an efficient emitter for the application of OLED applications. Furthermore, orange-red OLED devices based on TPAmCPPC exhibited a high EQEmax of 26.2%, a CE of 50.1 cd A-1, and a PE of 52.4 lm W-1.

Solution-processable organic light-emitting diodes utilizing electroluminescent perylene tetraester-based columnar liquid crystals.

Herein, we reveal a homologous series of liquid crystals involving perylene tetraesters as the core connected to the four trialkoxyphenyl units at the periphery using the triazole moiety as the linker. A thorough analysis using differential scanning calorimetry, polarized optical microscopy, and small- and wide-angle X-ray scattering studies confirm that all the mesogens 1a-c hold a stable enantiotropic columnar mesophase. Suitable molecular orbital levels and excellent material photophysical and thermal properties encouraged the study of their electroluminescent properties. Due to this, a well designed solution-processable organic light emitting diode device structure is configured as ITO (125 nm)/poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) (35 nm)/host: x wt% emitter (x = 0.5, 1.0, 3.0, 5.0) (20 nm)/2,2'2''-(1,3,5-benzinetriyl)tris(1-phenyl-1-H-benzimidazole) (TPBi) (40 nm)/lithium fluoride (LiF) (1 nm)/aluminium (Al) (200 nm) using compounds 1a-c as emitters. 4,4',4''-Tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA) and 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) were chosen as two different host materials. The current density-voltage-luminance and current efficacy-luminance-power efficacy plots suggest that m-MTDATA is a better host than CBP. Amongst, device based on 1 wt% emitter 1c doped in the m-MTDATA host matrix displayed the best performance, with a maximum power efficacy of 17.2 lm W-1, current efficacy of 18.5 cd A-1, and external quantum efficiency of 6.3%.

Main-chain engineering of polymer photocatalysts with hydrophilic non-conjugated segments for visible-light-driven hydrogen evolution.

Photocatalytic water splitting is attracting considerable interest because it enables the conversion of solar energy into hydrogen for use as a zero-emission fuel or chemical feedstock. Herein, we present a universal approach for inserting hydrophilic non-conjugated segments into the main-chain of conjugated polymers to produce a series of discontinuously conjugated polymer photocatalysts. Water can effectively be brought into the interior through these hydrophilic non-conjugated segments, resulting in effective water/polymer interfaces inside the bulk discontinuously conjugated polymers in both thin-film and solution. Discontinuously conjugated polymer with 10 mol% hexaethylene glycol-based hydrophilic segments achieves an apparent quantum yield of 17.82% under 460 nm monochromatic light irradiation in solution and a hydrogen evolution rate of 16.8 mmol m-2 h-1 in thin-film. Molecular dynamics simulations show a trend similar to that in experiments, corroborating that main-chain engineering increases the possibility of a water/polymer interaction. By introducing non-conjugated hydrophilic segments, the effective conjugation length is not altered, allowing discontinuously conjugated polymers to remain efficient photocatalysis.

Hydrophobic and Hydrophilic Conjugated Polymer Dots as Binary Photocatalysts for Enhanced Visible-Light-Driven Hydrogen Evolution through Förster Resonance Energy Transfer.

Organic semiconducting polymers exhibited promising photocatalytic behavior for hydrogen (H2) evolution, especially when prepared in the form of polymer dots (Pdots). However, the Pdot structures were formed using common nonconjugated amphiphilic polymers, which have a negative effect on charge transfer between photocatalysts and reactants and are unable to participate in the photocatalytic reaction. This study presents a new strategy for constructing binary Pdot photocatalysts by replacing the nonconjugated amphiphilic polymer typically employed in the preparation of polymer nanoparticles (Pdots) with a low-molecular-weight conjugated polyelectrolyte. The as-prepared polyelectrolyte/hydrophobic polymer-based binary Pdots truly enhance the electron transfer between the Pt cocatalyst and the polymer photocatalyst with good water dispersibility. Moreover, unlike the nonconjugated amphiphilic polymer, the photophysics and mechanism of this photocatalytic system through time-correlated single-photon counting (TCSPC) and transient absorption (TA) measurements confirmed the Förster resonance energy transfer (FRET) between the polyelectrolyte as a donor and the hydrophobic polymer as an acceptor. As a result, the designated binary Pdot photocatalysts significantly enhanced the hydrogen evolution rate (HER) of 43 900 µmol g-1 h-1 (63.5 µmol h-1, at 420 nm) for PTTPA/PFTBTA Pdots under visible-light irradiation.

Triarylamine-Pyridine-Carbonitriles for Organic Light-Emitting Devices with EQE Nearly 40.

Highly efficient thermally activated delayed fluorescence (TADF) molecules are in urgent demand for solid-state lighting and full-color displays. Here, the design and synthesis of three triarylamine-pyridine-carbonitrile-based TADF compounds, TPAPPC, TPAmPPC, and tTPAmPPC, are shown. They exhibit excellent photoluminescence quantum yields of 79-100% with small ΔEST values, fast reverse intersystem crossing (RISC), and high horizontal dipole ratios (Θ//  = 86-88%) in the thin films leading to the enhancement of device light outcoupling. Consequently, a green organic light-emitting diode (OLED) based on TPAmPPC shows a high average external quantum efficiency of 38.8 ± 0.6%, a current efficiency of 130.1 ± 2.1 cd A-1 , and a power efficiency of 136.3 ± 2.2 lm W-1 . The highest device efficiency of 39.8% appears to be record-breaking among TADF-based OLEDs to date. In addition, the TPAmPPC-based device shows superior operation lifetime and high-temperature resistance. It is worth noting that the TPA-PPC-based materials have excellent optical properties and the potential for making them strong candidates for TADF practical application.

Functional Pyrene-Pyridine-Integrated Hole-Transporting Materials for Solution-Processed OLEDs with Reduced Efficiency Roll-Off.

A series of new functional pyridine-appended pyrene derivatives, viz., 2,6-diphenyl-4-(pyren-1-yl)pyridine (Py-03), 2,6-bis(4-methoxyphenyl)-4-(pyren-1-yl)pyridine (Py-MeO), 4-(pyren-1-yl)-2,6-di-p-tolylpyridine (Py-Me), and 2,6-bis(4-bromophenyl)-4-(pyren-1-yl)pyridine (Py-Br) were designed, developed, and studied as the hole-transporting materials (HTMs) for organic light-emitting diode (OLED) application. The crystal structures of two molecules revealed to have a large dihedral angle between the pyrene and pyridine units, indicating poor π-electronic communication between them due to ineffective orbital overlap across the pyrene-pyridine systems as the two p-orbitals of pivotal atoms are twisted at 66.80° and 68.75° angles to each other in Py-03 and Py-Me, respectively. The influence of variedly functionalized pyridine units on the electro-optical properties and device performance of the present integrated system for OLED application was investigated. All of the materials have suitable HOMO values (5.6 eV) for hole injection by closely matching the HOMOs of indium tin oxide (ITO) and the light-emitting layer. All of the synthesized molecules have suitable triplet energies, glass transition temperatures, and melting temperatures, which are highly desirable for good HTMs. The pyrene-pyridine-based devices demonstrated stable performance with low-efficiency roll-off. The device with Py-Br as HTM showed a maximum luminance of 17300 cd/m2 with a maximum current efficiency of 22.4 cd/A and an EQE of 9% at 3500 cd/m2 with 7% roll-off from 1000 to 10 000 cd/m2. Also, the devices with Py-Me and Py-03 showed performance roll-up while moving from 1000 to 10 000 cd/m2.

Molecular Engineering for the Development of a Discotic Nematic Mesophase and Solid-State Emitter in Deep-Blue OLEDs.

A unique strategy for the attainment of a discotic nematic (ND) mesophase is reported consisting of a central benzene core to which are attached two 4-alkylphenyl and two 4-pentylbiphenyl moieties diagonally via alkynyl linkers. The rotational nature and incompatibility of unequal phenylethynyl units led to the disruption of π-π interactions within cores that aids to the realization of ND phase and favors high solid-state emission. When used in OLEDs, compounds act as an efficient solid-state pure deep-blue emitter with Commission Internationale de L'Eclairage (CIEx,y) coordinates of (0.16, 0.07).

Diboron-Based Delayed Fluorescent Emitters with Orange-to-Red Emission and Superior Organic Light-Emitting Diode Efficiency.

For the application of organic light-emitting diodes (OLEDs) in lighting and panels, the basic requirement is to include a full spectrum color range. Compared with the development of blue and green luminophores in thermally activated delayed fluorescence (TADF) technology, the progress of orange-to-red materials is slow and needs further investigation. In this study, three diboron compound-based materials, dPhADBA, dmAcDBA, and SpAcDBA, were designed and synthesized by nucleophilic arylation of three amine donors on 9,10-diboraanthracene (DBA) in a two-step reaction. With increasing electron-donating ability, they show orange-to-red emission with TADF characteristics. The electroluminescence of these diboron compounds exhibits emissions λmax at 613, 583, and 567 nm for dPhADBA, dmAcDBA, and SpAcDBA, respectively. It is noteworthy that the rod-like D-A-D structures can achieve high horizontal ratios (84-86%) and outstanding device performance for orange-to-red TADF OLEDs: the highest external quantum efficiencies for dPhADBA, dmAcDBA, and SpAcDBA are 11.1 ± 0.5, 24.9 ± 0.5, and 30.0 ± 0.8%, respectively. Therefore, these diboron-based molecules offer a promising avenue for the design of orange-to-red TADF emitters and the development of highly efficient orange-to-red OLEDs.

Cascade One-Pot Synthesis of Orange-Red-Fluorescent Polycyclic Cinnolino[2,3-f]phenanthridin-9-ium Salts by Palladium(II)-Catalyzed C-H Bond Activation of 2-Azobiaryl Compounds and Alkenes.

Quaternary ammonium salts were synthesized in moderate to good yields through double oxidative C-H bond activation on azobenzenes. The mechanism of the highly regioselective reaction of 2-azobiaryls with alkenes to give orange-red-fluorescent cinnolino[2,3-f]phenanthridin-9-ium salts and 15H-cinnolino[2,3-f]phenanthridin-9-ium-10-ide is proposed to involve ortho C-H olefination of the 2-azobiaryl compound with the alkene, intramolecular aza-Michael addition, concerted metalation-deprotonation (CMD), reductive elimination, and oxidation.

Quinolinylmethanone-Based Thermally Activated Delayed Fluorescence Emitters and the Application in OLEDs: Effect of Intramolecular H-Bonding.

Three new quinoline TADF emitters, 2QPM-mDC, 2QPM-mDTC, and 4QPM-mDTC, were designed and synthesized and the emitters show Δ EST as low as 0.07 eV and high PL quantum yield (PLQY) up to 98%. An electroluminescence device based on 2QPM-mDTC can reach high EQE over 24%. Compared with the reported TADF devices, the device shows narrow emission bandwidth and high color purity. The excellent device performance is likely ascribed to the molecular design of 2QPM-mDTC containing an intramolecular H-bonding in the molecule.

Pyridine-Carbonitrile-Carbazole-Based Delayed Fluorescence Materials with Highly Congested Structures and Excellent OLED Performance.

Three pyridine-carbonitrile-carbazole-based thermally activated delayed fluorescence (TADF) materials with highly sterically congested structures have been synthesized. The donor-acceptor-type TADF emitters (26-, 246-, and 35tCzPPC) consist of a 2,6-diphenylpyridine-3,5-dicarbonitrile core (PPC) as the acceptor and a di( t-butyl)carbazole-substituted phenyl group attached to C4 of the PC core as the donor. The molecules show a unique structure containing two consecutive large twisted angles along the donor and acceptor groups. The structure leads to a nearly complete space separation of the highest occupied molecular orbital and lowest unoccupied molecular orbital, a small Δ EST value, and excellent TADF property. Moreover, the 26- and 246tCzPPC dopants favor a horizontal alignment enhancing the light outcoupling of the device. In contrast, 35tCzPPC favors a perpendicular alignment reducing the light outcoupling efficiency of the device. The 246tCzPPC-based devices show external quantum efficiency as high as 29.6% because of excellent TADF property, very high photoluminescence quantum yield, and high Θ value in the thin films. The device performance is the best among the pyridine-carbonitrile-based TADF emitters.

Impact of the Valence Charge of Transition Metals on the Cobalt- and Rhodium-Catalyzed Synthesis of Indenamines, Indenols, and Isoquinolinium Salts: A Catalytic Cycle Involving MIII/MV [M = Co, Rh] for [4 + 2] Annulation.

Reaction mechanisms for the synthesis of indenamines, indenols, and isoquinolinium salts through cobalt- and rhodium-catalysis were investigated using density functional theory calculations. We found that the valence charge of transition metals dramatically influences the reaction pathways. Catalytic reactions involving lower-oxidation-state transition metals (MI/MIII, M = Co and Rh) generally favor a [3 + 2] cyclization pathway, whereas those involving higher oxidation states (MIII/MV) proceed through a [4 + 2] cyclization pathway. A catalytic cycle with novel MIII/MV as a crucial species was successfully revealed for isoquinolinium salts synthesis, in which highly valent MV was encountered not only in the [RhCp*]-catalysis but also in the [CoCp*]-catalysis.

Facile one-pot synthesis of 2,3-dihydro-1H-indolizinium derivatives by rhodium(iii)-catalyzed intramolecular oxidative annulation via C-H activation: application to ficuseptine synthesis.

Various substituted indolizidinium, quinolizinium and pyrido[1,2-a]azepinium salts synthesized from benzaldehydes (or α,ß-unsaturated aldehydes) and alkyne-amines catalyzed by rhodium complexes via C-H activation are demonstrated. The reaction was carried out under mild reaction conditions using Cu(BF4)2·6H2O as oxidant and anion source and inexpensive oxygen as a co-oxidant. A reaction mechanism involving imine formation followed by an ortho C-H activation, alkyne insertion and reductive elimination via a 7-membered rhodacycle is proposed. The present method has been successfully applied to the synthesis of a natural product, ficuseptine.

Direct Synthesis of Protoberberine Alkaloids by Rh-Catalyzed C-H Bond Activation as the Key Step.

A one-pot reaction of substituted benzaldehydes with alkyne-amines by a Rh-catalyzed C-H activation and annulation to afford various natural and unnatural protoberberine alkaloids is reported. This reaction provides a convenient route for the generation of a compound library of protoberberine salts, which recently have attracted great attention because of their diverse biological activities. In addition, pyridinium salt derivatives can also be formed in good yields from α,ß-unsaturated aldehydes and amino-alkynes. This reaction proceeds with excellent regioselectivity and good functional group compatibility under mild reaction conditions by using O2 as the oxidant.

Rhodium(III)-catalyzed vinylic C-H activation: a direct route toward pyridinium salts.

A synthetic method for highly substituted pyridinium salts from the multicomponent reaction of vinyl ketones/aldehydes, amines, and alkynes using a rhodium catalyst is demonstrated. The catalytic reaction proceeds via an in situ generated imine-assisted Rh(III)-catalyzed vinylic C-H activation.

One-pot synthesis of highly substituted polyheteroaromatic compounds by rhodium(III)-catalyzed multiple C-H activation and annulation.

A new method for the synthesis of highly substituted naphthyridine-based polyheteroaromatic compounds in high yields proceeds through rhodium(III)-catalyzed multiple C-H bond cleavage and C-C and C-N bond formation in a one-pot process. Such highly substituted polyheteroaromatic compounds have attracted much attention because of their unique π-conjugation, which make them suitable materials for organic semiconductors and luminescent materials. Furthermore, a possible mechanism, which involves multiple chelation-assisted ortho C-H activation, alkyne insertion, and reductive elimination, is proposed for this transformation.

Rh(III)-catalyzed synthesis of 1-substituted isoquinolinium salts via a C-H bond activation reaction of ketimines with alkynes.

An efficient synthesis of highly substituted isoquinolinium salts from ketimines and alkynes via a Rh(III)-catalyzed C-H bond activation and annulation reaction is described.