A Unique Blend of 2‐Fluorenyl‐2‐anthracene and 2‐Anthryl‐2‐anthracence Showing White Emission and High Charge Mobility

White‐light‐emitting materials with high mobility are necessary for organic white‐light‐emitting transistors, which can be used for self‐driven OLED displays or OLED lighting. In this study, we combined two materials with similar structures—2‐fluorenyl‐2‐anthracene (FlAnt) with blue emission and 2‐anthryl‐2‐anthracence (2A) with greenish‐yellow emission—to fabricate OLED devices, which showed unusual solid‐state white‐light emission with the CIE coordinates (0.33, 0.34) at 10 V. The similar crystal structures ensured that the OTFTs based on mixed FlAnt and 2A showed high mobility of 1.56 cm² V⁻¹ s⁻¹. This simple method provides new insight into the design of high‐performance white‐emitting transistor materials and structures.     

Computational Study on the Charge Transport and Optical Spectra of Anthracene Derivatives in Aggregates

A recent experiment [Angew. Chem. Int. Ed. 2017 , 56, 722–727] found that a (1 : 9) blend film of two anthracene derivatives, 2-fluorenyl-2-anthracene ( FlAnt ) and 2-anthryl-2-anthracence ( 2 A ), exhibit both efficient white light emission and high hole mobility, thus promising for organic light-emitting transistors (OLETs). Employing quantum chemistry at the polarizable continuum model (PCM) and the quantum mechanics/molecular mechanics (QM/MM) levels, we investigated the excited-state structures, optical spectra, band structure and the carrier mobility for FlAnt and 2 A from solution to aggregate phases. We suggest using the ratio of intermolecular excitonic coupling J and intramolecular excited state relaxation energy E to judge the bathochromic shift in optical emission in aggregates. For FlAnt , ρ=J/E is calculated to be less than 0.17, a critical value we identified earlier, and the spectra in solution and aggregate phases present quite similar features (blue emission). However, ρ is ∼0.5 for 2 A systems, and the calculated emission in the aggregate phase exhibits a remarkable bathochromic shift. In addition, the 0–0 emission is strongly suppressed in the herringbone stacking. These observations justify the experimental findings that (i) 2 A is blue emissive in solution but yellow-green in the aggregate phase, whereas FlAnt is always blue, and (ii) the blend of them show white emission. By using the “quantum nuclear tunneling” model we proposed earlier, we found the hole mobility for FlAnt and 2 A are 0.5 and 4.2 cm² V⁻¹ s⁻¹, respectively, indicating both are good hole transport materials.     

Dianthracenylazatrioxa[8]circulene: Synthesis,Characterization and Application in OLEDs

A soluble, green-blue fluorescent, π-extended azatrioxa[8]circulene was synthesized by oxidative condensation of a 3,6-dihydroxycarbazole and 1,4-anthraquinone by using benzofuran scaffolding. This is the first circulene to incorporate anthracene within its carbon framework. Solvent-dependent fluorescence and bright green electroluminescence accompanied by excimer emission are the key optical properties of this material. The presence of sliding π-stacked columns in the single crystal of dianthracenylazatrioxa[8]circulene is found to cause a very high electron-hopping rate, thus making this material a promising n-type organic semiconductor with an electron mobility predicted to be around 2.26 cm² V⁻¹ s⁻¹. The best organic light-emitting diode (OLED) device based on the dianthracenylazatrioxa[8]circulene fluorescent emitter has a brightness of around 16 000 Cd m⁻² and an external quantum efficiency of 3.3 %. Quantum dot-based OLEDs were fabricated by using dianthracenylazatrioxa[8]circulene as a host matrix material.     

Non‐Doped Sky‐Blue OLEDs Based on Simple Structured AIE Emitters with High Efficiencies at Low Driven Voltages

Blue organic light‐emitting diodes (OLEDs) are necessary for flat‐panel display technologies and lighting applications. To make more energy‐saving, low‐cost and long‐lasting OLEDs, efficient materials as well as simple structured devices are in high demand. However, a very limited number of blue OLEDs achieving high stability and color purity have been reported. Herein, three new sky‐blue emitters, 1,4,5‐triphenyl‐2‐(4‐(1,2,2‐triphenylvinyl)phenyl)‐1H‐imidazole (TPEI), 1‐(4‐methoxyphenyl)‐4,5‐diphenyl‐2‐(4‐(1,2,2‐triphenylvinyl)phenyl)‐1H‐imidazole (TPEMeOPhI) and 1‐phenyl‐2,4,5‐tris(4‐(1,2,2‐triphenylvinyl)phenyl)‐1H‐imidazole (3TPEI), with a combination of imidazole and tetraphenylethene groups, have been developed. High photoluminescence quantum yields are obtained for these materials. All derivatives have demonstrated aggregation‐induced emission (AIE) behavior, excellent thermal stability with high decomposition and glass transition temperatures. Non‐doped sky‐blue OLEDs with simple structure have been fabricated employing these materials as emitters and realized high efficiencies of 2.41 % (4.92 cd A⁻¹, 2.70 lm W⁻¹), 2.16 (4.33 cd A⁻¹, 2.59 lm W⁻¹) and 3.13 % (6.97 cd A⁻¹, 4.74 lm W⁻¹) for TPEI, TPEMeOPhI and 3TPEI, with small efficiency roll‐off. These are among excellent results for molecules constructed from the combination of imidazole and TPE reported so far. The high performance of a 3TPEI‐based device shows the promising potential of the combination of imidazole and AIEgen for synthesizing efficient electroluminescent materials for OLED devices.     

π-Extended Carbazole Derivatives as Host Materials for Highly Efficient and Long-Life Green Phosphorescent Organic Light-Emitting Diodes

High-performance organic light-emitting diodes (OLEDs) that use phosphorescent and/or thermally activated delayed fluorescence emitters are capable of realizing 100 % electron-to-photon conversion. The host materials in these OLEDs play crucial roles in determining OLED performance. Carbazole derivatives are frequently used as host materials, among which 3,3-bis(9H-carbazol-9-yl)biphenyl ( mCBP ) is often used for lifetime testing in scientific studies. In this study, the π conjugation of the carbazole unit was expanded to enhance OLED lifetime by designing and developing two benzothienocarbazole (BTCz)-based host materials, namely m1BTCBP and m4BTCBP . Among these host materials, m1BTCBP formed a highly efficient [Ir(ppy)₃]-based OLED with an operational luminescence half-life (LT₅₀) of over 300 h at an initial luminance of approximately 12000 cd m⁻² (current density: 25 mA cm⁻²). The LT₅₀ value at 1000 cd cm⁻² was estimated to be about 23 000 h. This performance is clearly higher than that of mCBP -based OLEDs (LT₅₀≈8500 h).     

Highly Emissive 9-Borafluorene Derivatives: Synthesis,Photophysical Properties and Device Fabrication

A series of 9-borafluorene derivatives, functionalised with electron-donating groups, have been prepared. Some of these 9-borafluorene compounds exhibit strong yellowish emission in solution and in the solid state with relatively high quantum yields (up to 73.6 % for FMesB-Cz as a neat film). The results suggest that the highly twisted donor groups suppress charge transfer, but the intrinsic photophysical properties of the 9-borafluorene systems remain. The new compounds showed enhanced stability towards the atmosphere, and exhibited excellent thermal stability, revealing their potential for application in materials science. Organic light-emitting diode (OLED) devices were fabricated with two of the highly emissive compounds, and they exhibited strong yellow-greenish electroluminescence, with a maximum luminance intensity of >22 000 cd m⁻². These are the first two examples of 9-borafluorene derivatives being used as light-emitting materials in OLED devices, and they have enabled us to achieve a balance between maintaining their intrinsic properties while improving their stability.     

Eutectic Molten Salt Synthesis of Highly Microporous Macrocyclic Porous Organic Polymers for CO2 Capture

The development of porous materials is of great interest for the capture of CO₂ from various emission sources, which is essential to mitigate its detrimental environmental impact. In this direction, porous organic polymers (POPs) have emerged as prime candidates owing to their structural tunability, physiochemical stability and high surface areas. In an effort to transfer an intrinsic property of a cyclotetrabenzoin-derived macrocycle – its high CO₂ affinity – into porous networks, herein we report the synthesis of three-dimensional (3D) macrocycle-based POPs through the polycondensation of an octaketone macrocycle with phenazine-2,3,7,8-tetraamine hydrochloride. This polycondensation was performed under ionothermal conditions, using a eutectic salt mixture in the temperature range of 200 to 300 °C. The resulting polymers, named 3D-mmPOPs, showed reaction temperature-dependent surface areas and gas uptake properties. 3D-mmPOP-250 synthesized at 250 °C exhibited a surface area of 752 m² g⁻¹ and high microporosity originating from the macrocyclic units, thus resulting in an excellent CO₂ binding enthalpy of 40.6 kJ mol⁻¹ and CO₂ uptake capacity of 3.51 mmol g⁻¹ at 273 K, 1.1 bar.     

Metal–Organic Frameworks and Other Crystalline Materials for Ultrahigh Superprotonic Conductivities of 10−2 S cm−1 or Higher

Proton-conducting materials in the solid state have received immense attention for their role as electrolytes in proton-exchange membrane fuel cells. Recently, crystalline materials—metal–organic frameworks (MOFs), hydrogen-bonded organic frameworks (HOFs), covalent organic frameworks (COFs), polyoxometalates (POMs), and porous organic crystals—have become an exciting research topic in the field of proton-conducting materials. For a better electrolyte, a high proton conductivity on the order of 10⁻² S cm⁻¹ or higher is preferred as efficient proton transport between the electrodes is ultimately necessary. With an emphasis on design principles, this Concept will focus on MOFs and other crystalline solid-based proton-conducting platforms that exhibit “ultrahigh superprotonic” conductivities with values in excess of 10⁻² S cm⁻¹. While only a handful of MOFs exhibit such an ultrahigh conductivity, this quality in other systems is even rarer. In addition to interpreting the structural–functional correlation by taking advantage of their crystalline nature, we address the challenges and promising directions for future research.     

Imidazo[1,2-a]pyridine as an Electron Acceptor to Construct High-Performance Deep-Blue Organic Light-Emitting Diodes with Negligible Efficiency Roll-Off

Two novel bipolar deep-blue fluorescent emitters, IP-PPI and IP-DPPI, featuring different lengths of the phenyl bridge, were designed and synthesized, in which imidazo[1,2-a]pyridine (IP) and phenanthroimidazole (PI) were proposed as an electron acceptor and an electron donor, respectively. Both of them exhibit outstanding thermal stability and high emission quantum yields. All the devices based on these two materials showed negligible efficiency roll-off with increasing current density. Impressively, non-doped organic light-emitting diodes (OLEDs) based on IP-PPI and IP-DPPI exhibited external quantum efficiencies (EQEs) of 4.85 % and 4.74 % with CIE coordinates of (0.153, 0.097) and (0.154, 0.114) at 10000 cd m⁻², respectively. In addition, the 40 wt % IP-PPI doped device maintained a high EQE of 5.23 % with CIE coordinates of (0.154, 0.077) at 10000 cd m⁻². The doped device based on 20 wt % IP-DPPI exhibited a higher deep-blue electroluminescence (EL) performance with a maximum EQE of up to 6.13 % at CIE of (0.153, 0.078) and maintained an EQE of 5.07 % at 10000 cd m⁻². To the best of our knowledge, these performances are among the state-of-the art devices with CIE_y≤0.08 at a high brightness of 10000 cd m⁻². Furthermore, by doping a red phosphorescent dye Ir(MDQ)₂ (MDQ=2-methyldibenzo[f,h]quinoxaline) into the IP-PPI and IP-DPPI hosts, high-performance red phosphorescent OLEDs with EQEs of 20.8 % and 19.1 % were achieved, respectively. This work may provide a new approach for designing highly efficient deep-blue emitters with negligible roll-off for OLED applications.     

Tunable Aggregation-Induced Emission of Imidazole Hydrazones by pH and Anions

Aggregation-induced emission (AIE) materials have drawn great attention for applications as organic light-emitting diodes (OLED) and probes. The applications are, however, restricted by the complex syntheses and hydrophobic properties. Herein, a one-step synthesis of an AIE material based on imidazole hydrazone is assessed. Protonation of the imidazole-H leads to emission color change from yellow to green in the solid state. The emission color is recovered upon imidazole-H⁺ deprotonation. Moreover, the emission wavelength shifts from 532 to 572 nm by anion exchange. In addition, an enhanced emission (Φ_F up to 22.6 %) was obtained with the Br⁻ anion compared with NTf₂⁻, SbCl₅⁻, PF₆⁻, and OTf⁻ anions. X-ray crystallography studies together with theoretical calculations show that the enhanced emission of hydrazone salts arises from strong hydrogen bonding between the hydrazone proton and the halide ion (Cl⁻ or Br⁻).     

2-对联苯-8-羟基喹啉锌的合成及其应用于新型白光OLED

合成了一种全新的有机发光材料2-对联苯-8-羟基喹啉锌(Zn[2-(p-biPh)-8-Q-O]₂), 通过¹H NMR, UV-Vis等对配合物的结构进行表征. 利用该材料制备了新型白光有机电致发光器件(OLED), 其结构为: ITO/NPB (N,N'-双(1-萘基)-N,N'-二苯基-1,1'-二苯基-4,4'-二胺)/BCP (2,9-二甲基-4,7-二苯基-1,10-菲咯啉)/Zn[2-(p-biPh)-8-Q-O]₂/Al. 通过调节空穴阻挡层BCP的厚度, 实现了NPB(蓝光发射)和Zn[2-(p-biPh)-8-Q-O]₂(黄光发射)作为器件双发光层的有效复合, 并研究了其发光机理. 当BCP层的厚度为2.0 nm时, 获得了稳定的白色发光; 该器件在6 V电压下启亮, 20 V电压时最大发光亮度达到130 cd/m², 电流效率为0.224 cd/A.     

Solution-Processable Unsymmetrical Triarylamines: Towards High Mobility and ON/OFF Ratio in Bottom-Gated OFETs

Self-assembly of organic small molecules into an ordered thin film has been the key strategy towards efficient charge transport for organic field-effect transistors (OFETs). Solution processing is a feasible and economic way to enhance pi–pi interaction. Herein, nitrile-substituted unsymmetrical triarylamines for OFET applications with high mobility are reported. The compounds were constructed by Suzuki cross-coupling reactions under inert conditions. The HOMO level of about 5.3 eV indicates good hole-transporting ability. OFETs were assembled in bottom-gate, top-contact architecture. Devices fabricated from a binary solvent system exhibited excellent p-channel characteristics, with impressively high charge-carrier mobility of up to 2.58 cm² V⁻¹ s⁻¹ and I_ON/OFF current ratios of 10⁶–10⁷. SEM and AFM analysis showed the efficient molecular self-assembly attained by the simple and effective solvent-engineering method. Theoretical insights obtained by DFT calculations supported by single-crystal structures showed that the crystalline nature and packing modes of these compounds ensure high mobility. The results prove that these compounds have great potential for use in numerous electronic applications, such as sensors and logic switches.     

Hierarchical FeCo2S4@FeNi2S4 Core/Shell Nanostructures on Ni Foam for High-Performance Supercapacitors

The design of electrode materials with rational core/shell structures is promising for improving the electrochemical properties of supercapacitors. Hence, hierarchical FeCo₂S₄@FeNi₂S₄ core/shell nanostructures on Ni foam were fabricated by a simple hydrothermal method. Owing to their structure and synergistic effect, they deliver an excellent specific capacitance of 2393 F g⁻¹ at 1 A g⁻¹ and long cycle lifespan as positive electrode materials. An asymmetric supercapacitor device with FeCo₂S₄@FeNi₂S₄ as positive electrode and graphene as negative electrode exhibited a specific capacitance of 133.2 F g⁻¹ at 1 A g⁻¹ and a high energy density of 47.37 W h kg⁻¹ at a power density of 800 W kg⁻¹. Moreover, the device showed remarkable cycling stability with 87.0 % specific-capacitance retention after 5000 cycles at 2 A g⁻¹. These results demonstrate that the hierarchical FeCo₂S₄@FeNi₂S₄ core/shell structures have great potential in the field of electrochemical energy storage.     

Electrophoretic Deposition of Binder‐Free MnO2/Graphene Films for Lithium‐Ion Batteries

Binder‐free, nano‐sized needlelike MnO₂ ‐submillimeter‐sized reduced graphene oxide (nMnO₂‐srGO ) hybrid films with abundant porous structures were fabricated through electrophoretic deposition and subsequent thermal annealing at 500 °C for 2 h. The as‐prepared hybrid films exhibit a unique hierarchical morphology, in which nMnO₂ with a diameter of 20—50 nm and a length of 300—500 nm is randomly anchored on both sides of srGO . When evaluated as binder‐free anodes for lithium‐ion half‐cell, the nMnO₂‐srGO composites with a content of 76.9 wt% MnO₂ deliver a high capacity of approximately 1652.2 mA •h•g⁻¹ at a current density of 0.1 A•g⁻¹ after 200 cycles. The high capacity remains at 616.8 mA •h•g⁻¹ (ca. 65.1% capacity retention) at a current density as high as 4 A•g⁻¹. The excellent electrochemical performance indicates that the nMnO₂‐srGO hybrid films could be a promising anode material for lithium ion batteries (LIBs ).     

Modulating the Electronic and Solid-State Structure of Organic Semiconductors by Site-Specific Substitution: The Case of Tetrafluoropentacenes

The properties as well as solid-state structures, singlet fission, and organic field-effect transistor (OFET) performance of three tetrafluoropentacenes (1,4,8,11: 10 , 1,4,9,10: 11 , 2,3,9,10: 12 ) are compared herein. The novel compounds 10 and 11 were synthesized in high purity from the corresponding 6,13-etheno-bridged precursors by reaction with dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate at elevated temperatures. Although most of the molecular properties of the compounds are similar, their chemical reactivity and crystal structures differ considerably. Isomer 10 undergoes the orbital symmetry forbidden thermal [4+4] dimerization, whereas 11 and 12 are much less reactive. The isomers 11 and 12 crystallize in a herringbone motif, but 10 prefers π–π stacking. Although the energy of the first electric dipole-allowed optical transition varies only within 370 cm⁻¹ (0.05 eV) for the neutral compounds, this amounts to roughly 1600 cm⁻¹ (0.20 eV) for radical cations and 1300 cm⁻¹ (0.16 eV) for dications. Transient spectroscopy of films of 11 and 12 reveals singlet-fission time constants (91±11, 73±3 fs, respectively) that are shorter than for pentacene (112±9 fs). OFET devices constructed from 11 and 12 show close to ideal thin-film transistor (TFT) characteristics with electron mobilities of 2×10⁻³ and 6×10⁻² cm² V⁻¹ s⁻¹, respectively.     

A hexaazatriphenylene-based porous organic polymer for high performance supercapacitor

Porous organic polymers (POPs) with high physiochemical stability and pseudocapacitive activity are crucial for supercapacitors with high specific capacitance and long cycle life. We report herein a hexaazatrinaphthylene-based POP (HPOP-1) for high-performance supercapacitor by introducing redox-active hexaazatrinaphthylene (HATN) moiety through Sonogashira–Hagihara coupling reaction. HATN moiety can undergo a proton-induced electron transfer redox reaction, which endows HPOP-1 with high pseudocapacitive activity. As electrode materials for supercapacitor application, HPOP-1 exhibits high specific capacitance (667 F g⁻¹ at 0.5 A g⁻¹) and long-term cyclic stability (90% capacitance retention after 10,000 cycles at 5 A g⁻¹) in a three-electrode system with 1 M H₂SO₄ as the electrolyte. In addition, HPOP-1 also exhibits a specific capacitance of 376 F g⁻¹ at 0.5 A g⁻¹ in 1 M KOH electrolyte. An asymmetric supercapacitor was further fabricated with HPOP-1 as negative electrode and rGO as positive electrode, respectively. The device delivers a specific capacitance of 63 F g⁻¹ at 0.5 A g⁻¹ and a rate performance of 37 F g⁻¹ at 5 A g⁻¹. Our work provides a facile approach for the design and preparation of pseudocapacitive POPs with high specific capacitance and long cycle life.     

Self-Assembled FeSe2 Microspheres with High-Rate Capability and Long-Term Stability as Anode Material for Sodium- and Potassium-Ion Batteries

Sodium- and potassium-ion batteries have attracted intensive attention recently as low-cost alternatives to lithium-ion batteries with naturally abundant resources. However, the large ionic radii of Na⁺ and K⁺ render their slow mobility, leading to sluggish diffusion in host materials. Herein, hierarchical FeSe₂ microspheres assembled by closely packed nano/microrods are rationally designed and synthesized through a facile solvothermal method. Without carbonaceous material incorporation, the electrode delivers a reversible Na⁺ storage capacity of 559 mA h g⁻¹ at a current rate of 0.1 A g⁻¹ and a remarkable rate performance with a capacity of 525 mA h g⁻¹ at 20 A g⁻¹. As for K⁺ storage, the FeSe₂ anode delivers a high reversible capacity of 393 mA h g⁻¹ at 0.4 A g⁻¹. Even at a high current rate of 5 A g⁻¹, a discharge capacity of 322 mA h g⁻¹ can be achieved, which is among the best high-rate anodes for K⁺ storage. The excellent electrochemical performance can be attributed to the favorable morphological structure and the use of an ether-based electrolyte during cycling. Moreover, quantitative study suggests a strong pseudocapacitive contribution, which boosts fast kinetics and interfacial storage.     

Tailoring Excited State Properties and Energy Levels Arrangement via Subtle Structural Design on D‐π‐A Materials

The donor‐π‐conjugated‐acceptor (D‐π‐A) structure is an important design for the luminescent materials because of its diversity in the selections of donor, π‐bridge and acceptor groups. Herein, we demonstrate two examples of D‐π‐A structures capable to finely modulate the excited state properties and arrangement of energy levels, TPA‐AN‐BP and CZP‐AN‐BP , which possess the same acceptor and π‐bridge but different donor. The investigation of their photophysical properties and DFT calculation revealed that the D‐π‐A structure with proper donor, π‐bridge and acceptor can result in separation of frontier molecular orbitals on the corresponding donor and acceptor with an obvious overlap on the π‐bridge, resulting in a hybridized local and charge‐transfer (HLCT ) excited state with high photoluminescent (PL ) efficiencies. Meanwhile, their singlet and triplet states are arranged on corresponding moieties with large energy gap between T₂ and T₁ , and a small energy gap between S₁ and T₂ , which favor the reverse intersystem crossing (RISC ) from high‐lying triplet levels to singlet levels. As a result, the sky‐blue emission non‐doped OLED based on the TPA‐AN‐BP reached maximum external quantum efficiency (EQE ) of 4.39% and a high exciton utilization efficiency (EUE ) of 77%. This study demonstrates a new strategy to construct highly efficient OLED materials.     

Near IR Bandgap Semiconducting 2D Conjugated Metal-Organic Framework with Rhombic Lattice and High Mobility

Two-dimensional conjugated metal–organic frameworks (2D c-MOFs) are emerging as a unique class of electronic materials. However, 2D c-MOFs with band gaps in the Vis-NIR and high charge carrier mobility are rare. Most of the reported conducting 2D c-MOFs are metallic (i.e. gapless), which largely limits their use in logic devices. Herein, we design a phenanthrotriphenylene-based, D_2h-symmetric π-extended ligand ( OHPTP ), and synthesize the first rhombic 2D c-MOF single crystals ( Cu₂(OHPTP) ). The continuous rotation electron diffraction (cRED) analysis unveils the orthorhombic crystal structure at the atomic level with a unique slipped AA stacking. The Cu₂(OHPTP) is a p-type semiconductor with an indirect band gap of ≈0.50 eV and exhibits high electrical conductivity of 0.10 S cm⁻¹ and high charge carrier mobility of ≈10.0 cm² V⁻¹ s⁻¹. Theoretical calculations underline the predominant role of the out-of-plane charge transport in this semiquinone-based 2D c-MOF.     

Surface plasmon spectroscopy of metal/dielectric structures

Surface electromagnetic waves (i.e. plasmons) were excited in metal—oxide—metal (MOM) multi-layer thin film structures by the tunnel current from an external dc source. Surface plasmons decayed to photons in the visible region with typically 10⁻¹⁰−10⁻¹²W cm⁻² light intensity.A very sensitive single channel optical spectrometer was constructed to study both spectral and angular distributions of light emitted from aluminum—oxide—noble-metal (Ag, Au, Cu) thin film diodes mounted into a cold-finger type liquid nitrogen optical cryostat. When MOM structures were prepared on substrates with regular surface modulation of 300–900 nm periods, spectral and angular measurements of the emitted light allowed one to construct the energy—wave-vector dispersion diagram of surface plasmons. This was of help in identifying the top meta/vacuum fast mode plasmons as the source of photon emission.