Optical Power Limiters Based on Colorless Di‐, Oligo‐, and Polymetallaynes: Highly Transparent Materials for Eye Protection Devices

The synthesis, characterization, and photophysics of a series of solution‐processable and tractable di‐, oligo‐, and polymetallaynes of some group 10–12 transition metals are presented. Most of these materials are colorless with very good optical transparencies in the visible spectral region and exhibit excellent optical power limiting (OPL) for nanosecond laser pulse. Their OPL responses outweigh those of the state‐of‐the‐art reverse saturable absorption dyes such as C₆₀, metalloporphyrins, and metallophthalocyanines that are all associated with very poor optical transparencies. On the basis of the results from photophysical studies and theoretical calculations, both the absorption of triplet and intramolecular charge‐transfer states can contribute to the enhancement of the OPL properties for these materials. Electronic influence of the type, spatial arrangement, and geometry of metal groups on the optical transparency/nonlinearity optimization is evaluated and discussed in detail. The positive contribution of transition metal ions to the OPL of these compounds generally follows the order: Pt > Au > Hg > Pd. The optical‐limiting thresholds for these polymetallaynes can be as low as 0.07 J cm^–2 at 92 % linear transmittance and these highly transparent materials manifest very impressive figure of merit σ_ex/σ_o values (up to 22.48), which are remarkably higher than those of the benchmark C₆₀ and metal phthalocyanine complexes. The present work demonstrates an attractive approach to developing materials offering superior OPL/optical transparency trade‐offs and these metallopolyynes are thus very promising candidates for use in practical OPL devices for the protection of human eyes and other delicate optical sensors.     

Preparation of Functional Hybrid Glass Material from Platinum (II) Complexes for Broadband Nonlinear Absorption of Light

The synthesis of trans‐di(arylalkynyl)diphosphine platinum(II) complexes bearing trialkoxysilane groups is described, as well as the preparation of siloxane‐based hybrid materials from organometallic chromophores through a modified sol–gel process. Glass materials prepared from trans‐[P(n–Bu)₃]₂Pt[(C≡C–p–C₆H₄–C≡C–p–C₆H₄–CH₂O(CO)NH(CH₂)₃Si(OC₂H₅)₃]₂ generally show spectral transmittance, absorption and luminescence similar to that of solutions reported in the literature. Measurements of optical power limiting for the hybrid glass are carried out, and show broadband nonlinear absorption throughout the whole visible wavelength range with clamping values in the range 0.2–7 µJ at 120 mM chromophore concentration. The sol–gel process using urethane‐propyltriethoxysilane‐functionalized chromophores as precursors appears to be a valid method for formation of robust silicate materials with grafted diarylethynyl Pt(II) complexes for OPL devices.     

Comparative Studies on Optical,Redox, and Photovoltaic Properties of a Series of D–A–D and Analogous D–A Chromophores

A series of new symmetrical donor‐acceptor‐donor (D?A?D) dyes based on s‐indacene‐1,3,5,7(2H,6H)‐tetraone as an acceptor unit containing varying electron donating moieties and analogous donor‐acceptor (D?A) chromophores with indane‐1,3‐dione as an acceptor are synthesized. By employing these two sets of dyes, the influence of a scaffold change from unsymmetric push‐pull (D?A) to symmetrical (D?A?D) systems on optical, electrochemical, and photovoltaic properties are explored. Detailed comparative studies reveal favorable optical characteristics and considerably decreased bandgaps for the D?A?D dyes compared to those of the reference D?A chromophores. Accordingly, the evaluation of the present dyes as donor materials in bulk heterojunction (BHJ) solar cells in combination with fullerene derivatives PC₆₁BM or PC₇₁BM as acceptors afforded significantly improved performance for devices based on D?A?D blends (up to a factor of 4 compared to the respective D‐A reference) with power conversion efficiencies of up to 2.8%. In less polar solvents such as toluene, some of the novel D?A?D chromophores exhibit unexpectedly high fluorescence quantum yields Φ_em of up to unity, in striking contrast to their weakly fluorescent D‐A counterparts.     

Nanoscale Organization of a Platinum(II) Acetylide Cholesteric Liquid Crystal Molecular Glass for Photonics Applications

The fabrication, molecular structure, and spectroscopy of a stable cholesteric liquid crystal platinum acetylide glass obtained from trans‐Pt(PEt₃)₂(C?C?C₆H₅?C?N)(C?C?C₆H₅?COO?Cholesterol), are described and designated as PE1‐CN‐Chol. Polarized optical microscopy, differential scanning calorimetry, and wide‐angle X‐ray scattering experiments show room temperature glassy/crystalline texture with crystal formation upon heating to 165 °C. Further heating results in conversion to cholesteric phase. Cooling to room temperature leads to the formation of a cholesteric liquid crystal glass. Scanning tunneling microscopy of a PE1‐CN‐Chol monolayer reveals self‐assembly at the solid?liquid interface with an array of two molecules arranged in pairs, oriented head‐to‐head through the CN groups, giving rise to a lamella arrangement. The lamella structure obtained from molecular dynamics calculations shows a clear phase separation between the conjugated platinum acetylide and the hydrophobic cholesterol moiety with the lamellae separation distance being 4.0 nm. Ultrafast transient absorption and flash photolysis spectra of the glass show intersystem crossing to the triplet state occurring within 100 ps following excitation. The triplet decay time of the film compared to aerated and deoxygenated solutions is consistent with oxygen quenching at the film surface but not within the film. The high chromophore concentration, high glass thermal stability, and long triplet lifetime in air show that these materials have potential as nonlinear absorbing materials.     

Functional Pyrimidinyl Pyrazolate Pt(II) Complexes: Role of Nitrogen Atom in Tuning the Solid‐State Stacking and Photophysics

Pt(II) metal complexes are known to exhibit strong solid‐state aggregation and are promising for realization of efficient emission in fabrication of organic light emitting diodes (OLED) with nondoped emitter layer. Four pyrimidine–pyrazolate based chelates, together with four isomeric Pt(II) metal complexes, namely: [Pt(pm2z)₂], [Pt(tpm2z)₂], [Pt(pm4z)₂], and [Pt(tpm4z)₂], are isolated and systematically investigated for their structure–property relationships for practical OLED applications. Detailed single molecular and aggregated structures are revealed by photophysical and mechanochromic measurements, grazing‐incidence X‐ray diffraction, and theoretical approaches. These results suggest that these Pt(II) emitters pack like a deck of playing cards under vacuum deposition, and their emission energy is not only affected by the single molecular designs, but notably influenced by their intermolecular packing interaction, i.e., Pt···Pt separations that are arranged in the order: [Pt(tpm4z)₂] > [Pt(pm4z)₂] > [Pt(tpm2z)₂] > [Pt(pm2z)₂]. Nondoped OLED with emission ranging from green to red are prepared, to which the best performances are recorded for [Pt(tpm2z)₂], giving maximum external quantum efficiency (EQE) of 27.5% at 10³ cd m^?2, maximum luminance of 2.5 × 10⁵ cd m^?2 at 17 V, and with stable CIE_x,y of (0.56, 0.44).     

Ultrasmall Pd‐Cu‐Pt Trimetallic Twin Icosahedrons Boost the Electrocatalytic Performance of Glycerol Oxidation at the Operating Temperature of Fuel Cells

Recently, in order to improve the energy conversion efficiency of direct polyol fuel cells, the engineering of effective Pd‐ and/or Pt‐based electrocatalysts to rupture C? C bonds has received increasing attention. Here, an example is shown to synthesize highly uniform sub‐10 nm Pd‐Cu‐Pt twin icosahedrons by controlling the nucleation phase. Because of the synergies of the electronic effect, synergistic effect, geometric effect, and abundant surface active sites originating from the formation of near surface alloy and special icosahedral shape, the Pd‐Cu‐Pt twin icosahedrons exhibit excellent electrocatalytic performance in glycerol electrocatalysis at the operating temperature of direct alcohol fuel cells (70 °C) in KOH electrolyte. The Pd_50.2Cu_38.4Pt_11.4 icosahedrons show mass activities of 9.7 A mg^?1_Pd+Pt and 13.7 A mg^?1_Pd. Furthermore, the Pd_50.2Cu_38.4Pt_11.4 icosahedrons demonstrate long‐term durability in current–time test for 36 000 s and high in situ anti‐CO poisoning performance. In addition, the introduction of CO can enhance electro‐oxidation endurance on Pd_50.2Cu_38.4Pt_11.4 icosahedrons, and the peak mass activity can reach to 14.4 A mg^?1_Pd+Pt. The in situ Fourier transform infrared spectroscopy spectra indicate that the Pd_50.2Cu_38.4Pt_11.4 icosahedrons possess a high capacity to break C? C bonds and may efficiently convert glycerol into CO₂, thus improving the utilization efficiency of energy‐containing molecule glycerol.     

High Efficiency White Organic Light‐Emitting Devices Incorporating Yellow Phosphorescent Platinum(II) Complex and Composite Blue Host

A new class of charge neutral, strongly luminescent cyclometalated platinum(II) complexes supported by dianionic tetradentate ligand are synthesized. One of these platinum(II) complexes, Y‐Pt , displays a high photoluminescence quantum yield of 86% and electroluminescence efficacy (η_power) of up to 52 lm W^?1, and is utilized as a yellow phosphorescent dopant in the fabrication of white organic light‐emitting devices (WOLEDs). WOLEDs based on conventional structures with yellow emission from Y‐Pt in combination with blue emission from bis(4,6‐difluorophenyl‐pyridinato‐N,C²′) (picolinate) iridium(III) (FIrpic) show a total η_power of up to 31 lm W^?1. A two‐fold increase in η_power by utilizing a modified WOLED structure comprising of a composite blue host is realized. With this modified device structure, the total η_power and driving voltage at a luminance of 1000 cd m^?2 can be improved to 61 lm W^?1 and 7.5 V (i.e., 10 V for control devices). The performance improvement is attributed to an effectively broaden exciton formation‐recombination zone and alleviation of localized exciton accumulation within the FIrpic‐doped composite host for reduced triplet‐triplet annihilation, yielding blue light‐emission with enhanced intensity. The modified device structure can also adopt a higher concentration of Y‐Pt towards its optimal value, leading to WOLEDs with high efficiency.     

Synthesis and Characterization of 2D Molybdenum Carbide (MXene)

Large scale synthesis and delamination of 2D Mo₂CT _x (where T is a surface termination group) has been achieved by selectively etching gallium from the recently discovered nanolaminated, ternary transition metal carbide Mo₂Ga₂C. Different synthesis and delamination routes result in different flake morphologies. The resistivity of free‐standing Mo₂CT _x films increases by an order of magnitude as the temperature is reduced from 300 to 10 K, suggesting semiconductor‐like behavior of this MXene, in contrast to Ti₃C₂T _x which exhibits metallic behavior. At 10 K, the magnetoresistance is positive. Additionally, changes in electronic transport are observed upon annealing of the films. When 2 μm thick films are tested as electrodes in supercapacitors, capacitances as high as 700 F cm^?3 in a 1 m sulfuric acid electrolyte and high capacity retention for at least 10,000 cycles at 10 A g^?1 are obtained. Free‐standing Mo₂CT _x films, with ≈8 wt% carbon nanotubes, perform well when tested as an electrode material for Li‐ions, especially at high rates. At 20 and 131 C cycling rates, stable reversible capacities of 250 and 76 mAh g^?1, respectively, are achieved for over 1000 cycles.     

Fully Transparent p‐MoTe2 2D Transistors Using Ultrathin MoOx/Pt Contact Media for Indium‐Tin‐Oxide Source/Drain

Since transition metal dichalcogenide (TMD) semiconductors are found as 2D van der Waals materials with a discrete energy bandgap, many 2D‐like thin field effect transistors (FETs) and PN diodes are reported as prototype electrical and optoelectronic devices. As a potential application of display electronics, transparent 2D FET devices are also reported recently. Such transparent 2D FETs are very few in report, yet no p‐type channel 2D‐like FETs are seen. Here, 2D‐like thin transparent p‐channel MoTe₂ FETs with oxygen (O₂) plasma‐induced MoO_x/Pt/indium‐tin‐oxide (ITO) contact are reported for the first time. For source/drain contact, 60 s short O₂ plasma and ultrathin Pt‐deposition processes on MoTe₂ surface are sequentially introduced before ITO thin film deposition and patterning. As a result, almost transparent 2D FETs are obtained with a decent mobility of ≈5 cm² V^?1 s^?1, a high ON/OFF current ratio of ≈10⁵, and 70% transmittance. In particular, for normal MoTe₂ FETs without ITO, O₂ plasma process greatly improves the hole injection efficiency and device mobility (≈60 cm² V^?1 s^?1), introducing ultrathin MoO_x between Pt source/drain and MoTe₂. As a final device application, a photovoltaic current modulator, where the transparent FET stably operates as gated by photovoltaic effects, is integrated.     

Ultrahigh Stability 3D TI Bi2Se3/MoO3 Thin Film Heterojunction Infrared Photodetector at Optical Communication Waveband

Infrared (IR) detection at 1300–1650 nm (optical communication waveband) is of great significance due to its wide range of applications in commerce and military. Three dimensional (3D) topological insulator (TI) Bi₂Se₃ is considered a promising candidate toward high‐performance IR applications. Nevertheless, the IR devices based on Bi₂Se₃ thin films are rarely reported. Here, a 3D TI Bi₂Se₃/MoO₃ thin film heterojunction photodetector is shown that possesses ultrahigh responsivity (R_i), external quantum efficiency (EQE), and detectivity (D*) in the broadband spectrum (405–1550 nm). The highest on–off ratio of the optimized device can reach up to 5.32 × 10⁴. R_i, D*, and the EQE can reach 1.6 × 10⁴ A W^?1, 5.79 × 10¹¹ cm² Hz^1/2 W^?1, and 4.9 × 10⁴% (@ 405 nm), respectively. Surprisingly, the R_i can achieve 2.61 × 10³ A W^?1 at an optical communication wavelength (@ 1310 nm) with a fast response time (63 µs), which is two orders of magnitude faster than that of other TIs‐based devices. In addition, the device demonstrates brilliant long‐term (>100 days) environmental stability under environmental conditions without any protective measures. Excellent device photoelectric properties illustrate that the 3D TI/inorganic heterojunction is an appropriate way for manufacturing high‐performance photodetectors in the optical communication, military, and imaging fields.     

Replicating the Defect Structures on Ultrathin Rh Nanowires with Pt to Achieve Superior Electrocatalytic Activity toward Ethanol Oxidation

Metal nanostructures with an ultrathin Pt skin and abundant surface defects are attractive for electrocatalytic applications owing to the increased utilization efficiency of Pt atoms and the presence of highly reactive sites. This paper reports a conformal, layer‐by‐layer deposition of Pt atoms on defective Rh nanowires for the faithful replication of surface defects (i.e., grain boundaries) on the Rh nanowires. The thickness of the Pt shell can be controlled from one monolayer up to 5.3 atomic layers. This series of Rh@Pt_nL (n = 1–5.3) core–sheath nanowires show greatly enhanced activity and durability in catalyzing the ethanol oxidation reaction in an acidic medium. Among others, the Rh @ Pt_3.5L nanowires show the greatest mass activity (809 mA mg^?1_Pt) and specific activity (1.18 mA cm^?2) after loaded on carbon support, which are 3.7 and 3.4 times those of the commercial Pt/C, respectively. In situ Fourier transform infrared spectroscopy studies indicate an enhanced interaction between the outermost Pt layer and the Rh nanowire can promote C? C bond cleavage for complete oxidation of ethanol to CO₂ while depress the dehydrogenation of ethanol to acetic acid. As the Pt shell thickness is increased, the selectivity for the CO₂ pathway decreases while that for acetic acid is increased.     

Low‐Threshold Distributed‐Feedback Lasers Based on Pyrene‐Cored Starburst Molecules with 1,3,6,8‐Attached Oligo(9,9‐Dialkylfluorene) Arms

Here, a detailed characterization of the optical gain properties of sky‐blue‐light‐emitting pyrene‐cored 9,9‐dialkylfluorene starbursts is reported; it is shown that these materials possess encouragingly low laser thresholds and relatively high thermal and environmental stability. The materials exhibit high solid‐state photoluminescence (PL) quantum efficiencies (>90%) and near‐single‐exponential PL decay transients with excited state lifetimes of ～1.4 ns. The thin‐film slab waveguide amplified spontaneous emission (ASE)‐measured net gain reaches 75–78 cm^?1. The ASE threshold energy is found to remain unaffected by heating at temperatures up to 130 °C, 40 to 50 °C above T_g. The ASE remained observable for annealing temperatures up to 170 or 200 °C. 1D distributed feedback lasers with 75% fill factor and 320 nm period show optical pumping thresholds down to 38–65 Wcm^?2, laser slope efficiencies up to 3.9%, and wavelength tuning ranges of ～40 nm around 471–512 nm. In addition, these lasers have relatively long operational lifetimes, with N_1/2 ≥ 1.1 × 10⁵ pulses for unencapsulated devices operated at ten times threshold in air.     

Enhancing Phosphorescence and Electrophosphorescence Efficiency of Cyclometalated Pt(II) Compounds with Triarylboron

A synthetic strategy for the preparation of cyclometalated platinum(II) acetylacetonate (acac) complexes functionalized with triarylboron is achieved. This method is used to synthesize a series of triarylboron‐functionalized phosphorescent Pt(acac) compounds, which are characterized by NMR spectroscopy, X‐ray crystallography, and theoretical calculations. These complexes exhibit a range of bright phosphorescent colors spanning the green to red region of the visible spectrum (λ_max = ～520–650 nm) in solution and the solid state. Functionalization with a triarylboron group leads to significant enhancement in quantum yield for several of these complexes relative to the non‐borylated Pt(II) parent chromophores, which may be attributed to the increased mixing of ¹MLCT and ³LC states. The phosphorescent enhancement, electron transport capabilities, and steric bulkiness offered by the triarylboron group can be used to significantly enhance the performance of electrophosphorescent devices based on Pt(II) emitters. A high efficiency green electrophosphorescent device is fabricated with a maximum external quantum efficiency of 8.9%, luminance efficiency of 34.5 cd A^?1, and power efficiency of 29.8 lm W^?1, giving significantly improved performance over control devices in which the Pt(II) emitter lacks the boron functionality.     

Plasmonic Heterostructure TiO2‐MCs/WO3−x‐NWs with Continuous Photoelectron Injection Boosting Hot Electron for Methane Generation

Nonmetallic plasmonic heterostructure TiO₂‐mesocrystals/WO_3?x‐nanowires (TiO₂‐MCs/WO_3?x‐NWs) are constructed by coupling mesoporous crystal TiO₂ and plasmonic WO_3?x through a solvothermal procedure. The continuous photoelectron injection from TiO₂ stabilizes the free carrier density and leads to strong surface plasmon resonance (SPR) of WO_3?x, resulting in strong light absorption in the visible and near‐infrared region. Photocatalytic hydrogen generation of TiO₂‐MCs/WO_3?x‐NWs is attributed to plasmonic hot electrons excited on WO_3?x‐NWs under visible light irradiation. However, utilization of injected photoelectrons on WO_3?x‐NWs has low efficiency for hydrogen generation and a co‐catalyst (Pt) is necessary. TiO₂‐MCs/WO_3?x‐NWs are used as co‐catalyst free plasmonic photocatalysts for CO₂ reduction, which exhibit much higher activity (16.3 µmol g^?1 h^?1) and selectivity (83%) than TiO₂‐MCs (3.5 µmol g^?1 h^?1, 42%) and WO_3?x‐NWs (8.0 µmol g^?1 h^?1, 64%) for methane generation under UV–vis light irradiation. A photoluminescence study demonstrates the photoelectron injection from TiO₂ to WO_3?x, and the nonmetallic SPR of WO_3?x plays a great role in the highly selective methane generation during CO₂ photoreduction.     

Precious‐Metal‐Free Electrocatalysts for Activation of Hydrogen Evolution with Nonmetallic Electron Donor: Chemical Composition Controllable Phosphorous Doped Vanadium Carbide MXene

The insufficient strategies to improve electronic transport, the poor intrinsic chemical activities, and limited active site densities are all factors inhibiting MXenes from their electrocatalytic applications in terms of hydrogen production. Herein, these limitations are overcome by tunable interfacial chemical doping with a nonmetallic electron donor, i.e., phosphorization through simple heat‐treatment with triphenyl phosphine (TPP) as a phosphorous source in 2D vanadium carbide MXene. Through this process, substitution, and/or doping of phosphorous occurs at the basal plane with controllable chemical compositions (3.83–4.84 at%). Density functional theory (DFT) calculations demonstrate that the P? C bonding shows the lowest surface formation energy (ΔG_Surf) of 0.027 eV Å^?2 and Gibbs free energy (ΔG_H) of –0.02 eV, whereas others such as P‐oxide and P? V (phosphide) show highly positive ΔG_H. The P3–V₂CT_x treated at 500 °C shows the highest concentration of P? C bonds, and exhibits the lowest onset overpotential of –28 mV, Tafel slope of 74 mV dec^?1, and the smallest overpotential of ‐163 mV at 10 mA cm^?2 in 0.5 m H₂SO₄. The first strategy for electrocatalytically accelerating hydrogen evolution activity of V₂CT_x MXene by simple interfacial doping will open the possibility of manipulating the catalytic performance of various MXenes.     

Ordered Mesoporous Metastable α‐MoC1−x with Enhanced Water Dissociation Capability for Boosting Alkaline Hydrogen Evolution Activity

The sluggish reaction kinetics of the alkaline hydrogen evolution reaction (HER) remains an important challenge for water–alkali electrolyzers, which originates predominantly from the additional water dissociation step required for the alkaline HER. In this work, it is demonstrated theoretically and experimentally that metastable, face‐centered‐cubic α‐MoC_1?x phase shows superior water dissociation capability and alkaline HER activity than stable, hexagonal‐close‐packed Mo₂C phase. Next, high surface area ordered mesoporous α‐MoC_1?x (MMC) is designed via a nanocasting method. In MMC structure, the α‐MoC_1?x phase facilitates the water dissociation reaction, while the mesoporous structure with high surface area enables a high dispersion of metal NPs and efficient mass transport. As a result, Pt nanoparticles (NPs) supported on MMC (Pt/MMC) show substantially enhanced alkaline HER activity in terms of overpotentials, Tafel slopes, mass and specific activities, and exchange current densities, compared to commercial Pt/C and Pt NPs supported on particulate α‐MoC_1?x or β‐Mo₂C. Notably, Pt/MMC shows very low Tafel slope of 30 mV dec^–1, which is the lowest value among the reported Pt‐based alkaline HER catalysts, suggesting the critical role of MMC in enhancing the HER kinetics. The promotional effect of MMC support in the alkaline HER is further demonstrated with an Ir/MMC catalyst.     

Substituent Effects on Crosslike Packing of 2′,7′‐Diaryl‐ spiro(cyclopropane‐1,9′‐fluorene) Derivatives: Synthesis and Crystallographic,Optical, and Thermal Properties

A series of 2′,7′‐diarylspiro(cyclopropane‐1,9′‐fluorene) derivatives are efficiently synthesized and characterized to determine the reason for the “green‐light” emission of these compounds. These compounds exhibit bright‐violet to blue photoluminescence (PL) (λ^PL_max = 353–419 nm) with excellent PL quantum efficiencies (Φ_PL = 83–100 %) in solution and show high thermal stabilities (T_d = 267–474 °C). The variation of the optical properties of these molecules in the solid state depends on the different stacking modes of these compounds containing different substituents, which are revealed by crystallographic analysis. CH…π hydrogen bonds instead of intermolecular π–π interactions act as the driving force between adjacent fluorenes, even though a very small dialkyl group (cyclopropane) is introduced at the C‐9 position of fluorene. The crosslike molecular stacking efficiently reduces the energy transfer between the herring‐like aggregates and therefore results in the absence of a “green‐light” emission tail. In order to determine the cause of the “green‐light” emission tails, the fluorescence spectra of the films annealed in N₂ or in air are recorded. Broad green‐light emission tails were observed for the films annealed in air, which might be caused by fluorenone defects generated during processing or during the course of the photophysical analysis by reaction with residual oxygen.     

New Organic Nonlinear Optical Polyene Crystals and Their Unusual Phase Transitions

A series of new nonlinear optical chromophores based on configurationally locked polyenes (CLPs) with chiral pyrrolidine donors are synthesized. All CLP derivatives exhibit high thermal stability with decomposition temperatures T_d at least > 270 °C. Acentric single crystals of enantiopure D ‐ and L ‐prolinol‐based chromophores with a monoclinic space group P2₁ exhibit a macroscopic second‐order nonlinearity that is twice as large than that of analogous dimethylamino‐based crystal. This is attributed to a strong hydrogen‐bonded polar polymer‐like chain built by these molecules, which is aligned along the polar crystallographic b‐axis. Five α‐phase CLP crystals with different donors grown from solution exhibit a reversible or irreversible thermally induced structural phase transition to a β‐phase. These phase transitions are unusual, changing the crystal symmetry from higher to lower at increasing temperatures, for example, from centrosymmetric to non‐centrosymmetric, enhancing their macroscopic second‐order nonlinear optical properties.     

Phosphorescent Cationic Au4Ag2 Alkynyl Cluster Complexes for Efficient Solution‐Processed Organic Light‐Emitting Diodes

Cationic Au₄Ag₂ heterohexanuclear aromatic acetylides cluster complexes supported by bis(2‐diphenylphosphinoethyl)phenylphosphine (dpep) are prepared. The Au₄Ag₂ cluster structure originating from the combination of one anionic [Au(C≡CR)₂]^? with one cationic [Au₃Ag₂(dpep)₂(C≡CR)₂]³⁺ through the formation of Ag?acetylide η²‐bonds is highly stabilized by Au–Ag and Au–Au contacts. The Au₄Ag₂ alkynyl cluster complexes are moderately phosphorescent in the fluid CH₂Cl₂ solution, but exhibit highly intense phosphorescent emission in solid state and film. As revealed by theoretical computational studies, the phosphorescence is ascribable to significant ³[π (aromatic acetylide) → s/p (Au)] ³LMCT parentage with a noticeable Au₄Ag₂ cluster centered ³[d → s/p] triplet state. Taking advantage of mCP and OXD‐7 as a mixed host with 20 wt% dopant of phosphorescent Au₄Ag₂ cluster complex in the emitting layer, solution‐processed organic light‐emitting diodes (OLEDs) exhibit highly efficient electrophosphorescence with the maximum current, power, and external quantum efficiencies of 24.1 cd A^?1, 11.6 lm W^?1, and 7.0%, respectively. Introducing copper(I) thiocyanate (CuSCN) as a hole‐transporting layer onto the PEDOT:PSS hole‐injecting layer through the orthogonal solution process induces an obvious improvement of the device performance with lower turn‐on voltage and higher electroluminescent efficiency.     

An Effective Approach to Achieve a Spin Gapless Semiconductor–Half‐Metal–Metal Transition in Zigzag Graphene Nanoribbons: Attaching A Floating Induced Dipole Field via π–π Interactions

Under first‐principles computations, a simple strategy is identified to modulate the electronic and magnetic properties of zigzag graphene nanoribbons (zGNRs). This strategy takes advantage of the effect of the floating dipole field attached to zGNRs via π–π interactions. This dipole field is induced by the acceptor/donor functional groups, which decorate the ladder‐structure polydiacetylene derivatives with an excellent delocalized π‐conjugated backbone. By tuning the acceptor/donor groups, –C≡C– number, and zGNR width, greatly enriched electronic and magnetic properties, e.g., spin gapless semiconducting, half‐metallic, and metallic behaviors, with the antiferromagnetic?ferromagnetic conversion can be achieved in zGNRs with perfect, 57‐reconstructed, and partially hydrogenated edge patterns.