Single-Component Color-Tunable Smart Organic Emitters with Simultaneous Multistage Stimuli-Responsiveness and Multimode Emissions.

Achieving color-tunable emission in single-component organic emitters with multistage stimuli-responsiveness is of vital significance for intelligent optoelectronic applications, but remains enormously challenging. Herein, we present an unprecedented example of a color-tunable single-component smart organic emitter (DDOP) that simultaneously exhibits multistage stimuli-responsiveness and multimode emissions. DDOP based on a highly twisted amide-bridged donor-acceptor-donor structure has been found to facilitate intersystem crossing, form multimode emissions, and generate multiple emissive species with multistage stimuli-responsiveness. DDOP pristine crystalline powders exhibit abnormal excitation-dependent emissions from a monomer-dominated blue emission centered at 470 nm to a dimer-dominated yellow emission centered at 550 nm through decreasing the ultraviolet (UV) excitation wavelengths, whereas DDOP single crystals show a wide emission band with a main emission peak at 585 nm when excited at different wavelengths. The emission behaviors of pristine crystalline powders and single crystals are different, demonstrating emission features that are closely related to the aggregation states. The work has developed color-tunable single-component organic emitters with simultaneous multistage stimuli-responsiveness and multimode emissions, which is vital for expanding intelligent optoelectronic applications, including multilevel information encryption, multicolor emissive patterns, and visual monitoring of UV wavelengths.

A Polyzwitterion-Mediated Polymer Electrolyte with High Oxidative Stability for Lithium-Metal Batteries.

To achieve high-performance solid-state lithium-metal batteries (SSLMBs), solid electrolytes with high ionic conductivity, high oxidative stability, and high mechanical strength are necessary. However, balancing these characteristics remains dramatically challenging and is still not well addressed. Herein, a simple yet effective design strategy is presented for the development of high-performance polymer electrolytes (PEs) by exploring the synergistic effect between dynamic H-bonded networks and conductive zwitterionic nanochannels. Multiple weak intermolecular interactions along with ample nanochannels lead to high oxidative stability (over 5 V), improved mechanical properties (strain of 1320%), and fast ion transport (ionic conductivity of 10-4 S cm-1 ) of PEs. The amphoteric ionic functional units also effectively regulate the lithium ion distribution and confine the anion transport to achieve uniform lithium ion deposition. As a result, the assembled SSLMBs exhibit excellent capacity retention and long-term cycle stability (average Coulombic efficiency: 99.5%, >1000 cycles with LiFePO4 cathode; initial capacity: 202 mAh g-1 , average Coulombic efficiency: 96%, >230 cycles with LiNi0.8 Co0.1 Mn0.1 O2 cathode). It is exciting to note that the corresponding flexible cells can be cycled stably and can withstand severe deformation. The resulting polyzwitterion-mediated PE therefore offers great promise for the next-generation safe and high-energy-density flexible energy storage devices.

Improved electroluminescence efficiency derived from functionalized decoration of 1,3,4-oxadiazole (OXD)-based Ir(III) complexes.

The performance of organic light emitting devices (OLEDs) fabricated using Ir(III) complexes bearing 1,3,4-oxadiazole (OXD)-based cyclometallic ligands still needs to be improved. In this work, Ir3+ was coordinated with a 2-(9,9-diethyl-9H-fluoren-2-yl)-1,3,4-oxadiazole (F-OXD) fragment, which was modified with various functionalized substituents, including fluorenyl, OXD and carbazolyl groups. Three complexes, named Ir-Flu, Ir-OXD and Ir-Cz, were synthesized successfully and their photophysical, electrochemical and electroluminescence properties were investigated in detail. All these complexes exhibited yellow-orange emission in solution and a distinct aggregation-induced phosphorescent emission (AIPE) phenomenon was observed. Monochrome OLEDs were fabricated using these phosphorescent dopants, and the turn-on voltage (V), luminance (L) and current efficiency (CE) showed significant improvement compared to analogous OXD-based Ir(III) complexes reported before. In particular, the device with Ir-OXD as the dopant achieved the highest maximum brightness of 25 014 cd m-2 and the lowest efficiency roll-off (42.6%) at the maximum luminance among all the devices. These results provided a proven strategy of functionalized decoration of OXD-based complexes to achieve superior luminous efficiency devices.

Intrinsically Stretchable Electroluminescent Elastomers with Self-Confinement Effect for Highly Efficient Non-Blended Stretchable OLEDs.

Ultra-flexible stretchable organic light-emitting diodes (OLEDs) are emerging as a basic component of flexible electronics and human-machine interfaces. However, the brightness and efficiency of stretchable OLEDs remain still far inferior to their rigid counterparts, owing to the scarcity of satisfactory stretchable electroluminescent materials. Herein, we explore a general concept based on the self-confinement effect to dramatically improve the stretchability of elastomers, without affecting electroluminescent properties. The balanced rigid/flexible chain dynamics under self-confinement significantly reduces the modulus of the elastomers, resulting in the maximum strain reaching 806 %. Ultra-flexible stretchable OLEDs have been constructed based on the resulting ISEEs, achieving unprecedented high-performance non-blended stretchable OLEDs. The results suggest an effective molecular design strategy for highly deformable stretchable displays and flexible electronics.

Constructing Lithium-Free Anode/Separator Interface via 3D Carbon Fabric Scaffold for Ultrasafe Lithium Metal Batteries.

Metallic lithium represents a promising anode candidate to be utilized in future high-energy lithium batteries. However, the undesirable dendrite growth and fragile solid-electrolyte interphase (SEI) pose critical challenge for pursuing further practical application. In contrast to traditional approaches of using inert/lithiophilicity coating, here, we demonstrate a reverse strategy of introducing a highly conductive and lithophobic carbon fabric (CF) scaffold on lithium foil to guide a favorable nucleation site of lithium far away from the anode/separator interface. The CF scaffold with high conductivity can couple with inner electric field for achieving a uniform distribution of the lithium-ion flux, while the lithophobic feature offers the condition to guide the preferred deposition of lithium onto the underlying lithium foil, which greatly reduces the risk of dendrite-induced short circuits. Moreover, the SEI immersed in the CF scaffold is well supported by CF fibers and therefore exhibits extremely high stability during charge-discharge cycles. As a result, the lithium/CF anodes show >2,000-h stable cycling at 0.5 mA cm-2. Lithium metal batteries equipped with our lithium/CF anode deliver a high capacity retention of ~99.99% per cycle, i.e., retain ~97.3% capacity after 200 cycles. The unique interface-regulation strategy is versatile for various conductive scaffolds (e.g., ultrathin and ultralight conductive fabrics), exhibiting high superiority for highly safe lithium metal batteries.

Wireless Human-Machine Interface Based on Artificial Bionic Skin with Damage Reconfiguration and Multisensing Capabilities.

Human-machine interfaces (HMIs) enable users to interact with machines, thus playing a significant role in artificial intelligence, virtual reality, and the metaverse. Conventional HMIs are based on bulky and rigid electronic devices, seriously limiting their ductility, damage reconfiguration, and multifunctionality. In terms of replacing conventional HMIs, artificial bionic skins with good ductility, self-reparation, and multisensory ability are promising candidates. Still, they in their present form require innovations in mechanical and sensory properties, especially damage recovery and environmental stability, which seriously affect the service life and result in tons of electric waste. Herein, we present a new type of artificial bionic skin with excellent mechanical performance (>13,000% strain), high environmental stability (-80 to 80 °C), and multiple sensory properties toward strain, stress, temperature, solvent, and bioelectricity. Besides, this new type of artificial bionic skin also exhibits effective reconfiguration ability after damage and recyclability. The as-prepared artificial bionic skin was used as an interactive HMI to collect and distinguish the different sensory stimuli. The electronics assembled by HMI with artificial bionic skin can adhere compliantly on the human body for wireless motion capturing and sensing via Bluetooth, Wi-Fi, and the Internet. With simple programming, complex human motions can be mimicked in real-time by robots.

Tuning the Circularly Polarized Luminescence of Supramolecules via Self-Assembly Morphology Control.

Tuning the circularly polarized luminescence (CPL) is a paramount yet challenging issue in the research field of chiral materials. Here, the chiral supramolecules were constructed with a chiral inducer LL-diphenylalanine (LPFF) and a triphenyl-1,3,5-triazine-derived achiral molecule (DMAC-TRZ) to generate differentiated aggregates, giving rise to tunable responses of CPL. Specifically, the well-defined supercrystallines had an exceptional superior CPL emission located at 485 nm with a large luminescence dissymmetry factor (glum) value as high as +0.16, whereas the formed organic gel possessed a relatively strong CPL emission peaked at 495 nm with a glum value of -0.04 in respect to the water fraction about 50%. The distinguished glum value was assigned to the choice of spatial arrangement of the π-chromophores of DMAC-TRZ responding to the volume water fraction in the H2O/DMSO system, resulting in a tunable glum value. This strategy provides an efficient way to regulate CPL signals by modulating the π-stacking way of organic materials responding to external stimuli.

Discriminating Chiral Supramolecular Motions by Circularly Polarized Luminescence.

Molecular motions are closely associated with the behaviors and properties of organic materials. However, monitoring molecular motions is challenging. Herein, a chiral supramolecular system consisting of L-/D-phenylalanine (LPF/DPF) as a chiral inducer and an achiral tetraphenylethene derivative (TPEF) as a molecular rotor has been proposed and explored for real-time discriminating the supramolecular motions by the visualization of circularly polarized luminescence (CPL) signal variations. Derived from the ordered molecular motions of TPEF induced by LPF/DPF, highly organized aggregates have been progressively assembled in a controlled manner with differentiated morphologies, including spherical particles, one-dimensional fibers, and floor-shaped supercrystals. Notably, increasing level of ordered aggregates, in turn, led to quenching emissions, while the CPL signals have been dramatically amplified accompanying by a sharp enhancement of luminescence dissymmetry factors (glum ) from nearly 0 to -0.1. The significant amplification of CPL is attributed to the ordered aggregates of supramolecules, leading to the decrease of electric transition dipole moments in supramolecular system. As a result of the chiral supramolecular motions powered by supramolecular crystallization, the supramolecular motions are conveniently discriminated by visual CPL signal variation with an enhancement of glum value from 0 to -0.1 in real time.

Advanced Current Collector Materials for High-Performance Lithium Metal Anodes.

Lithium metal, as the "Holy Grail" of lithium battery anodes, is promising to be used in the next-generation of high-energy-density storage devices. However, serious safety risk and poor cycle performance are inevitable when bare lithium foil is used as the anode material, due to the uncontrolled growth of lithium dendrites, unstable solid electrolyte interface, and infinite volume expansion of lithium during cycling, which largely hinder the further commercial application of lithium metal batteries (LMBs). The utilization of up-to-date current collectors with specific composition and structure is believed to be effective to overcome these shortcomings. However, a systematic evaluation of the merit of different current collector materials for realizing high-performance lithium metal anodes is still lacking. This review summarizes the fashionable advanced current collector materials for long-life LMBs in recent years. The superiorities and related electrochemical performances by using these current collector materials are discussed in detail. It is expected that this review may promote the rational choice of appreciatory current collector materials with unique structure designs to extend the cycle life of lithium metal anodes for achieving the next-generation of high-energy-density LMBs.

Porous organic polymers for high-performance supercapacitors.

With the aim of addressing the global warming issue and fossil energy shortage, eco-friendly and sustainable renewable energy technologies are urgently needed. In comparison to energy conversion, studies on energy storage fall behind and remain largely to be explored. By storing energy from electrochemical processes at the electrode surface, supercapacitors (SCs) bridge the performance gap between electrostatic double-layer capacitors and batteries. Organic electrode materials have drawn extensive attention because of their special power density, good round trip efficiency and excellent cycle stability. Porous organic polymers (POPs) have drawn extensive attention as attractive electrode materials in SCs. In this review, we present and discuss recent advancements and design principles of POPs as efficient electrode materials for SCs from the perspectives of synthetic strategies and the structure-performance relationships of POPs. Finally, we put forward the outlook and prospects of POPs for SCs.

Frequency-Upconverted Stimulated Emission by Up to Six-Photon Excitation from Highly Extended Spiro-Fused Ladder-Type Oligo(p-phenylene)s.

Frequency-upconverted fluorescence and stimulated emission induced by multiphoton absorption (MPA) have attracted much interest. As compared with low-order MPA processes, the construction of high-order MPA processes is highly desirable and rather attractive, yet remains a formidable challenge due to its inherent low transition probability. We report the observation of the first experimental frequency-upconverted fluorescence and stimulated emission by simultaneous six-photon excitation in an organic molecular system. The well-designed organic conjugated system based on cross-shaped spiro-fused ladder-type oligo(p-phenylene)s (SpL-z, z=1-3) manifests reasonably high MPA cross-sections and brilliant luminescence emission simultaneously. The six-photon absorption cross-section of SpL-3 with an extended π-conjugation was evaluated as 8.67×10-169  cm12 s5 photon-5 . Exceptionally efficient 2- to 6-photon excited stimulated emission was achieved under near-infrared laser excitation.

Self-templated synthesis of uniform hollow spheres based on highly conjugated three-dimensional covalent organic frameworks.

Covalent organic frameworks (COFs) have served as a family of porous crystalline molecules for various promising applications. However, controllable synthesis of COFs with uniform morphology is paramount yet still remains quite challenging. Herein, we report self-templated synthesis of uniform and unique hollow spheres based on highly conjugated three-dimensional (3D) COFs with diameters of 500-700 nm. A detailed time-dependent study reveals the continuous transformation from initial nano sphere-like particles into uniform hollow spherical structures with Ostwald ripening mechanism. Particularly, the resulting 3D COF (3D-Sp-COF) is prone to transport ions more efficiently and the lithium-ion transference number (t+) of 3D-Sp-COF reaches 0.7, which even overwhelms most typical PEO-based polymer electrolytes. Inspiringly, the hollow spherical structures show enhanced capacitance performance with a specific capacitance of 251 F g-1 at 0.5 A g-1, which compares favorably with the vast majority of two-dimensional COFs and other porous electrode materials.

Highly Regioselective Direct C-H Arylation: Facile Construction of Symmetrical Dithienophthalimide-Based π-Conjugated Molecules for Optoelectronics.

Controllable direct C-H arylation with high regioselectivity is highly desirable yet remains a formidable challenge. Herein, a facile regioselective direct C-H arylation is developed for efficient construction of a variety of symmetrical dithienophthalimide-based π-conjugated molecules. The resulting methodology is applicable to a wide range of substrates, from electron-rich units to electron-deficient units with large steric end groups. Aryl halides have been confirmed to be able to couple with dithienophthalimide (DTI) via direct C-H arylation, showing high regioselectivity. Varying the functional end groups onto the DTI core has been demonstrated to fine tune the emission colors to cover most of the visible spectra. The results suggest a facile strategy towards highly selective direct C-H arylation, opening the prospects towards efficient construction of π-conjugated molecules for various potential optoelectronic applications.

Organic solid-state lasers: a materials view and future development.

Lasing applications have spread over various aspects of human life. To meet the developing trends of the laser industry towards being miniature, portable, and highly integrated, new laser technologies are in urgent demand. Organic semiconductors are promising gain medium candidates for novel laser devices, due to their convenient processing techniques, ease of spectral and chemical tuning, low refractive indexes, mechanical flexibilities, and low thresholds, etc. organic solid-state lasers (OSSLs) open up a new horizon of simple, low-cost, time-saving, versatile and environmental-friendly manufacturing technologies for new and desirable laser structures (micro-, asymmetric, flexible, etc.) to unleash the full potential of semiconductor lasers for future electronics. Besides the development of optical feedback structures, the design and synthesis of robust organic gain media is critical as a vigorous aspect of OSSLs. Herein, we provide a comprehensive review of recent advances in organic gain materials, mainly focused on organic semiconductors for OSSLs. The significant breakthroughs toward electrical pumping of OSSLs are emphasized. Opportunities, challenges and future research directions for the design of organic gain media are also discussed.

Boosting Circularly Polarized Luminescence of Organic Conjugated Systems via Twisted Intramolecular Charge Transfer.

Realizing a high luminescence dissymmetry factor (g lum) is a paramount yet challenging issue in the research field of circularly polarized luminescence (CPL). Here, we reported a novel set of organic conjugated systems with twisted intramolecular charge transfer (TICT) characteristics based on conjugated o-carborane-binaphthyl dyads composing of binaphthyl units as chiral electron donors and o-carborane units as achiral electron acceptors, demonstrating intense CPL with large g lum values. Interestingly, single-crystalline o-1 exhibited a high-level brightness and a large g lum factor as high as +0.13, whereas single-crystalline o-2 processed a relatively low brightness with a decreased g lum value to -0.04. The significant diversity of CPL-active properties was triggered by the selective introduction of o-carborane units onto the binaphthyl units. Benefiting from the large magnetic dipole transition moments in TICT states, the CPL activity of TICT o-carborane-based materials exhibited amplified circular polarization. This study provides an efficient molecular engineering strategy for the rational design and development of highly efficient CPL-active materials.

Donor-Acceptor Type Pendant Conjugated Molecules Based on a Triazine Center with Depressed Intramolecular Charge Transfer Characteristics as Gain Media for Organic Semiconductor Lasers.

A set of fluorene-capped pendant conjugated molecules (T-m and T-p), which consist of a triazine center with three carbazole substituents as the donor-acceptor (D-A) type pendant structure, were designed, synthesized, and investigated as gain media for organic semiconductor lasers (OSLs). In particular, varying the capping positions of the fluorene units on the pendant core structures results in significantly different intramolecular charge transfer (ICT) properties, where T-m manifested depressed ICT characteristic and high fluorescence quantum yield. The lowest amplified spontaneous emission (ASE) threshold in neat films was recorded as 1.9 µJ cm-2 for T-m and 83.8 µJ cm-2 for T-p, which indicated that the depressed ICT characteristics in the case of T-m help to enhance the ASE properties. Remarkably, the ASE threshold remained almost unchanged and the ASE spectra showed very small shifts (within 1 nm) for T-m with film samples annealed up to 180 °C in open air. In contrast, its linear counterpart 2FEtCz-m showed a clearly increased ASE threshold upon annealing above 100 °C. The results suggest that the selective construction of conjugated pendant molecules with depressed ICT characteristics is beneficial for finely modulating the optical and electrical properties as well as improving the thermostability and photostability, which manifests the great potential as a robust gain media for OSLs.

Diindolotriazatruxene-Based Hole-Transporting Materials for High-Efficiency Planar Perovskite Solar Cells.

A novel set of hole-transporting materials (HTMs) based on π-extended diindolotriazatruxene (DIT) core structure with electron-rich methoxy-engineered functional groups were designed and synthesized via a facile two-step procedure. All compounds were afforded from inexpensive precursors without a complex purification process. Cyclic voltammograms indicate that the resulting HTMs exhibit suitable highest occupied molecular orbital (HOMO) energy levels, which facilitate efficient hole injection from the valence band of perovskites into the HOMO of DIT-based HTMs as confirmed by time-resolved photoluminescence. Notable power conversion efficiency of the planar perovskite solar cells with low-temperature device fabrication achieved 18.21% utilizing D2, which is competitive with the corresponding devices based on the common Spiro-OMeTAD-based HTMs. The results manifest that DIT-based compounds are promising HTMs for constructing high-efficiency planar perovskite solar cells with low-cost solution processing procedures.

Low-Threshold Non-Doped Deep Blue Lasing from Monodisperse Truxene-Cored Conjugated Starbursts with High Photostability.

Herein, the photophysical, morphological, optical gain characteristics of a set of trigonal monodisperse starburst conjugated macromolecules (Tr1-Tr4) have been systematically investigated in order to elucidate the influence of the molecular structures on their optoelectronic performance. With increasing the oligofluorene arm length, absorption spectra were red-shifted progressively, whereas an increase in photoluminescence quantum yields (PLQYs) and optical gain coefficients, and a corresponding reduction in amplified spontaneous emission (ASE) thresholds and loss coefficients were observed for Tr1-Tr3 except for Tr4. The results indicate that the effective conjugation length become saturated for Tr3 in this system. Impressively, the resulting molecules manifested very low ASE thresholds (4.4-11.6 µJ cm-2 ) with high photostability, as well as high thermal stability. One dimensional distributed feedback (DFB) lasers exhibited a minimum lasing threshold of 10.38 nJ pulse-1 (0.86 kW cm-2 , 4.325 µJ cm-2 ) for Tr3. It should be emphasized that the ASE threshold of Tr1-Tr4 was nearly unchanged from room temperature to 200 °C. The results suggest that this kind of truxene-cored conjugated starbursts with high photostability and low lasing thresholds are rather promising gain media for organic semiconductor lasers.

Inkjet-Printed High-Performance Flexible Micro-Supercapacitors with Porous Nanofiber-Like Electrode Structures.

Flexible planar micro-supercapacitors (MSCs) with unique loose and porous nanofiber-like electrode structures are fabricated by combining electrochemical deposition with inkjet printing. Benefiting from the resulting porous nanofiber-like structures, the areal capacitance of the inkjet-printed flexible planar MSCs is obviously enhanced to 46.6 mF cm-2 , which is among the highest values ever reported for MSCs. The complicated fabrication process is successfully averted as compared with previously reported best-performing planar MSCs. Besides excellent electrochemical performance, the resultant MSCs also show superior mechanical flexibility. The as-fabricated MSCs can be highly bent to 180° 1000 times with the capacitance retention still up to 86.8%. Intriguingly, because of the remarkable patterning capability of inkjet printing, various modular MSCs in serial and in parallel can be directly and facilely inkjet-printed without using external metal interconnects and tedious procedures. As a consequence, the electrochemical performance can be largely enhanced to better meet the demands of practical applications. Additionally, flexible serial MSCs with exquisite and aesthetic patterns are also inkjet-printed, showing great potential in fashionable wearable electronics. The results suggest a feasible strategy for the facile and cost-effective fabrication of high-performance flexible MSCs via inkjet printing.

Iridium(III)-Complexed Polydendrimers for Inkjet-Printing OLEDs: The Influence of Solubilizing Steric Hindrance Groups.

With the great success of organic light-emitting diodes (OLEDs) based on thermal evaporation techniques, the development of printable materials for inkjet-printing high-performance OLEDs is particularly attractive yet challenging. In this paper, a set of printable Ir(III)-complexed polydendrimers, poly[bis[2-(2,4-difluorophenyl)-4-(4-((2-ethylhexyl)oxy)phenyl)pyridine][1-ethyl-5-phenyl-3-propyl-1H-1,2,4-triazole] iridium(III)] (PIr-D1) and poly[bis[2-(2,4-difluorophenyl)-4-(4-((2-ethylhexyl)oxy)-2,6-dimethylphenyl)pyridine][1-methyl-5-phenyl-3-propyl-1H-1,2,4-triazole] iridium(III)] (PIr-D2), were designed and synthesized via ring-opening metathesis polymerization (ROMP). As a comparison, the iridium precursor complexes bis[2-(2,4-difluorophenyl)-4-(4-((2-ethylhexyl)oxy)phenyl)pyridine][1-methyl-5-phenyl-3-propyl-1H-1,2,4-triazole]iridium(III) (Ir-D1) and bis[2-(2,4-difluorophenyl)-4-(4-((2-ethylhexyl)oxy)-2,6-dimethylphenyl)pyridine][1-methyl-5-phenyl-3-propyl-1H-1,2,4-triazole] iridium(III) (Ir-D2) and the core structure bis[2-(2,4-difluorophenyl)pyridine] [1-methyl-5-phenyl-3-propyl-1H-1,2,4-triazole] iridium(III) (Ir-D0) were also synthesized and the corresponding OLEDs were fabricated. Compared with the dendritic iridium complexes Ir-D1 and Ir-D2, the resulting polydendrimers PIr-D2 and PIr-D2 showed enhanced film-forming properties, good thermal stability, and attractive ink rheological characteristics with a suitable viscosity for inkjet-printing. Promising device performance has been achieved for the resulting polydendrimers by both spin-coating and inkjet-printing, showing low driving voltages and relatively high current efficiencies and brightnesses. The results suggest that the construction of polydendritic Ir(III) complexes is an attractive design strategy for exploring efficient printable light-emitting materials for inkjet-printing high-performance OLEDs.