J-Aggregate Promoting NIR-II Emission for Fluorescence/Photoacoustic Imaging-Guided Phototherapy.

J-aggregate is a promising strategy to enhance second near-infrared window (NIR-II) emission, while the controlled synthesis of J-aggregated NIR-II dyes is a huge challenge because of the lack of molecular design principle. Herein, bulk spiro[fluorene-9,9'-xanthene] functionalized benzobisthiadiazole-based NIR-II dyes (named BSFX-BBT and OSFX-BBT) are synthesized with different alkyl chains. The weak repulsion interaction between the donor and acceptor units and the S…N secondary interactions make the dyes to adopt a co-planar molecular conformation and display a peak absorption >880 nm in solution. Importantly, BSFX-BBT can form a desiring J-aggregate in the condensed state, and femtosecond transient absorption spectra reveal that the excited states of J-aggregate are the radiative states, and J-aggregate can facilitate stimulated emission. Consequently, the J-aggregated nanoparticles (NPs) display a peak emission at 1124 nm with a high relative quantum yield of 0.81%. The efficient NIR-II emission, good photothermal effect, and biocompatibility make the J-aggregated NPs demonstrate efficient antitumor efficacy via fluorescence/photoacoustic imaging-guided phototherapy. The paradigm illustrates that tuning the aggregate states of NIR-II dye via spiro-functionalized strategy is an effective approach to enhance photo-theranostic performance.

Charge-Localized Retention and Long-Term Memory Enabled by Cooperating Sterically Confined Molecular Crystallization with Spiro[fluorene-9,9'-xanthene]-Based Csp3-Hindrance.

Charge localization of memory materials plays a crucial role in the endurance and retention ability of organic nonvolatile memory, which is completely opposite from the charge delocalization of high-mobility materials. However, charge transfer of both though-space and through-bond based on molecular design principles still faces challenges. Herein, a nonplanar wide-bandgap semiconductor with Csp3-hindrance (DOCH3-DDPA-SFX) has been designed and synthesized. An effective crystallization effect of self-assembled two-dimensional nanosheets on charge trapping dynamics and kinetics is visualized by Kelvin probe force microscopy (KPFM). The trapped charges are localized completely on a single nanosheet, which has better charge trapping and retention properties than an amorphous film. Meanwhile, crystallization also greatly improves structure stability. Combining DFT theoretical calculations, the mechanisms of localization and long-term retention are discussed. The steric crystallization effects on the charge localization will guide the effective design of single-component semiconducting charge-memory materials by molecular assembly and aggregate control for high-performance organic memory.

Flexible molecular crystals for optoelectronic applications.

The cornerstones of the advancement of flexible optoelectronics are the design, preparation, and utilization of novel materials with favorable mechanical and advanced optoelectronic properties. Molecular crystalline materials have emerged as a class of underexplored yet promising materials due to the reduced grain boundaries and defects anticipated to provide enhanced photoelectric characteristics. An inherent drawback that has precluded wider implementation of molecular crystals thus far, however, has been their brittleness, which renders them incapable of ensuring mechanical compliance required for even simple elastic or plastic deformation of the device. It is perplexing that despite a plethora of reports that have in the meantime become available underpinning the flexibility of molecular crystals, the "discovery" of elastically or plastically deformable crystals remains limited to cases of serendipitous and laborious trial-and-error approaches, a situation that calls for a systematic and thorough assessment of these properties and their correlation with the structure. This review provides a comprehensive and concise overview of the current understanding of the origins of crystal flexibility, the working mechanisms of deformations such as plastic and elastic bending behaviors, and insights into the examples of flexible molecular crystals, specifically concerning photoelectronic changes that occur in deformed crystals. We hope this summary will provide a reference for future experimental and computational efforts with flexible molecular crystals aimed towards improving their mechanical behavior and optoelectronic properties, ultimately intending to advance the flexible optoelectronic technology.

Tuning the Absorption, Fluorescence, Intramolecular Charge Transfer, and Intersystem Crossing in Spiro[fluorene]acridinone.

In this work, we prepared a series of electron donor-acceptor systems based on spiro[fluorene-9,7'-dibenzo[c,h]acridine]-5'-one (SFDBAO). Our SFDBAOs consist of orthogonally positioned fluorenes and aromatic ketones. By fine-tuning the substitution of electron-donating pyrenes, the complex interplay among different excited-state decay channels and the overall impact of solvents on these decay channels were uncovered. Placing pyrene, for example, at the aromatic ketones resulted in a profound solvatochromism in the form of a bright charge-transfer (CT) emission spanning from yellow to red-NIR. In contrast, a dark non-emissive CT was noted upon pyrene substitution at the fluorenes. In apolar solvents, efficient triplet-excited state generation was observed for all SFDBAOs. Either charge transfer was concluded to mediate the intersystem crossing (ISC) in the case of pyrene substitution or the El-Sayed rule was applicable when lacking pyrene substitution as in the case of SFABAO. In polar solvents, charge separation is the sole decay upon pyrene substitution. Moreover, competition between ISC and CT lowered the triplet-excited state generation in SFDBAO.

17O solid-state NMR study on exposed facets of ZnO nanorods with different aspect ratios.

The physical and chemical properties of metal oxide nanocrystals are closely related to their exposed facets, so the study on facet structures is helpful to develop facet/morphology-property relationships and rationally design nanostructures with desired properties. In this study, wurtzite ZnO nanorods with different aspect ratios were prepared by controlling the Zn2+/OH- ratio, temperature and time in hydrothermal processes. An 17O solid-state NMR study was performed on these nanorods, after surface 17O labeling, to explore the relationship of the 17O NMR signals with the local surface structure of different exposed facets, i.e., nonpolar (101̄0) and polar (0002) facets. It is observed that, one of the signals, the sharp component of a peak at -18.8 ppm, comprises the contribution from the oxygen ions on the polar (0002) facets, in addition to that from nonpolar (101̄0) facets, which is confirmed by 17O NMR spectra of ZnO nanorods with controlled aspect ratios and different thermal treatment conditions. This is important for accurately interpreting the 17O NMR signal of ZnO-containing materials, especially when studying the facet-related mechanisms. The method applied here can also be extended to study the facet-dependent properties of other faceted oxide nanocrystals.

Coplanar Conformational Structure of π-Conjugated Polymers for Optoelectronic Applications.

Hierarchical structure of conjugated polymers is critical to dominating their optoelectronic properties and applications. Compared to nonplanar conformational segments, coplanar conformational segments of conjugated polymers (CPs) demonstrate favorable properties for applications as a semiconductor. Herein, recent developments in the coplanar conformational structure of CPs for optoelectronic devices are summarized. First, this review comprehensively summarizes the unique properties of planar conformational structures. Second, the characteristics of the coplanar conformation in terms of optoelectrical properties and other polymer physics characteristics are emphasized. Five primary characterization methods for investigating the complanate backbone structures are illustrated, providing a systematical toolbox for studying this specific conformation. Third, internal and external conditions for inducing the coplanar conformational structure are presented, offering guidelines for designing this conformation. Fourth, the optoelectronic applications of this segment, such as light-emitting diodes, solar cells, and field-effect transistors, are briefly summarized. Finally, a conclusion and outlook for the coplanar conformational segment regarding molecular design and applications are provided.

Follistatin-like 1 protects endothelial function in the spontaneously hypertensive rat by inhibition of endoplasmic reticulum stress through AMPK-dependent mechanism.

OBJECTIVE: Endothelial dysfunction is a critical initiating factor in the development of hypertension and related complications. Follistatin-like 1 (FSTL1) can promote endothelial cell function and stimulates revascularization in response to ischemic insult. However, it is unclear whether FSTL1 has an effect on ameliorating endothelial dysfunction in spontaneously hypertensive rats (SHRs). METHODS: Wistar Kyoto (WKY) and SHRs were treated with a tail vein injection of vehicle (1 mL/day) or recombinant FSTL1 (100 µg/kg body weight/day) for 4 weeks. Blood pressure was measured by tail-cuff plethysmograph, and vascular reactivity in mesenteric arteries was measured using wire myography. RESULTS: We found that treatment with FSTL1 reversed impaired endothelium-dependent relaxation (EDR) in mesenteric arteries and lowered blood pressure of SHRs. Decreased AMP-activated protein kinase (AMPK) phosphorylation, elevated endoplasmic reticulum (ER) stress markers, increased reactive oxygen species (ROS), and reduction of nitric oxide (NO) production in mesenteric arteries of SHRs were also reversed by FSTL1 treatment. Ex vivo treatment with FSTL1 improved the impaired EDR in mesenteric arteries from SHRs and reversed tunicamycin (ER stress inducer)-induced ER stress and the impairment of EDR in mesenteric arteries from WKY rats. The effects of FSTL1 were abolished by cotreatment of compound C (AMPK inhibitor). CONCLUSIONS: These results suggest that FSTL1 prevents endothelial dysfunction in mesenteric arteries of SHRs through inhibiting ER stress and ROS and increasing NO production via activation of AMPK signaling.

Li+ mobility powered by a crystal compound for fast Li-S chemistry.

Placing blocking layers between electrodes has shown paramount prospects in suppressing the shuttle effect of Li-S batteries, but the associated ionic transport would be a concurrent obstacle. Herein, we present a Li-based crystal composited with carbon (LiPN2@C) by a one-step annealing of Li+ absorbed melamine polyphosphate, which simultaneously achieves alleviated polysulfide-shuttling and facilitated Li+ transport. As a homologous crystal, LiPN2 with abundant lithiophilic sites makes Li+ transport more efficient and sustainable. With a LiPN2@C-modified separator, the Li2S cathode exhibits a much-lower activation potential of 2.4 V and a high-rate capacity of 519 mA h g-1 at 2C. Impressively, the battery delivers a capacity of 726 mA h g-1 at 0.5C with a low decay rate of 0.25% per cycle during 100 continuous cycles.

One-Pot Synthesis and Excited-State Dynamics of Null Exciton-Coupled Diketopyrrolopyrroles Oligo-Grids.

Exciton coupling in molecular aggregates plays a vital role in impacting and fine-tuning optoelectronic materials and their efficiencies in devices. A versatile platform to decipher aggregation-property relationships is built around multichromophoric architectures. Here, a series of cyclic diketopyrrolopyrrole (DPP) oligomers featuring nanoscale gridarene structures and rigid bifluorenyl spacers are designed and synthesized via one-pot Friedel-Crafts reaction. DPP dimer [2]Grid and trimer [3]Grid, which are cyclic rigid nanoarchitectures of rather different sizes, are further characterized via steady-state and time-resolved absorption and fluorescence spectroscopies. They exhibit monomer-like spectroscopic signatures in the steady-state measurements, from which null exciton couplings are derived. Moreover, in an apolar solvent, high fluorescence quantum yields and excited-state dynamics that resembled DPP monomer are gathered. In a polar solvent, the localized singlet excited state on a single DPP dissociates into the adjacent null coupling DPP with charge transfer characteristics. This pathway facilitates the evolution of the symmetry-broken charge-separated state (SB-CS). Notable is the fact that the SB-CS of [2]Grid is, on one hand, in equilibrium with the singlet excited state and promotes, on the other hand, the formation of the triplet excited state with a yield of 32% via charge recombination.

Structure-Property Relationship of Macrocycles in Organic Photoelectric Devices: A Comprehensive Review.

Macrocycles have attracted significant attention from academia due to their various applications in organic field-effect transistors, organic light-emitting diodes, organic photovoltaics, and dye-sensitized solar cells. Despite the existence of reports on the application of macrocycles in organic optoelectronic devices, these reports are mainly limited to analyzing the structure-property relationship of a particular type of macrocyclic structure, and a systematic discussion on the structure-property is still lacking. Herein, we conducted a comprehensive analysis of a series of macrocycle structures to identify the key factors that affect the structure-property relationship between macrocycles and their optoelectronic device properties, including energy level structure, structural stability, film-forming property, skeleton rigidity, inherent pore structure, spatial hindrance, exclusion of perturbing end-effects, macrocycle size-dependent effects, and fullerene-like charge transport characteristics. These macrocycles exhibit thin-film and single-crystal hole mobility up to 10 and 26.8 cm2 V-1 s-1, respectively, as well as a unique macrocyclization-induced emission enhancement property. A clear understanding of the structure-property relationship between macrocycles and optoelectronic device performance, as well as the creation of novel macrocycle structures such as organic nanogridarenes, may pave the way for high-performance organic optoelectronic devices.

Regulating and Predicting the Polyhedral Crystal Morphology in Spirofluorene Molecular Systems.

Crystallization of organic steric molecules often leads to multiple polyhedral crystal morphologies. However, the relationships among the molecular structure, supramolecular interaction, aggregation mode and crystal morphology are still unclear. In this work, we elaborate two model crystals formed by spiro[fluorene-9,9'-xanthene] (SFX) and spiro[cyclopenta[1,2-b : 5,4-b']dipyridine-5,9'-xanthene] (SDAFX) to demonstrate the feasibility of morphology prediction by periodic bond chain (PBC) theory based on interaction energy (IE) values in terms of single point energy. With non-directional van der Waals forces, only one PBC direction is found in SFX crystal, leading to the irregular 1D rod-like structure. Compared with SFX, the extra N heteroatoms in SDAFX can bring additional hydrogen bonds and some other interactions into the bulky molecular skeletons, inducing 3-dimensionally oriented PBCs to form the explicit F-face network in SDAFX which leads to the final octahedral structure. A simple and accurate method has been provided to quantify PBC vector on the supramolecular level in the organic molecular system, and the PBC theory has also been further demonstrated and developed in the morphology prediction of organic spiro-molecules.

Large-Scale Synthesis of Hierarchical Porous MOF Particles via a Gelation Process for High Areal Capacitance Supercapacitors.

Metal-organic frameworks (MOFs) with hierarchical porous structures have been attracting intense interest currently due to their promising applications in catalysis, energy storage, drug delivery, and photocatalysis. Current fabrication methods usually employ template-assisted synthesis or thermal annealing at high temperatures. However, large-scale production of hierarchical porous metal-organic framework (MOF) particles with a simple procedure and mild condition is still a challenge, which hampers their application. To address this issue, we proposed a gelation-based production method and achieved hierarchical porous zeolitic imidazolate framework-67 (called HP-ZIF67-G thereafter) particles conveniently. This method is based on a metal-organic gelation process through a mechanically stimulated wet chemical reaction of metal ions and ligands. The interior of the gel system is composed of small nano and submicron ZIF-67 particles as well as the employed solvent. The relatively large pore size of the graded pore channels spontaneously formed during the growth process is conducive to the increased transfer rate of substances within the particles. It is proposed that the Brownian motion amplitude of the solute is greatly reduced in the gel state, which leads to porous defects inside the nanoparticles. Furthermore, HP-ZIF67-G nanoparticles interwoven with polyaniline (PANI) exhibited an exceptional electrochemical charge storage performance with an areal capacitance of 2500 mF cm-2, surpassing those of many MOF materials. This stimulates new studies on MOF-based gel systems to obtain hierarchical porous metal-organic frameworks which should benefit further applications in a wide spectrum of fields ranging from fundamental research to industrial applications.

Hierarchical Nanoarchitectonics of Ultrathin 2D Organic Nanosheets for Aqueous Processed Electroluminescent Devices.

Ultrathin 2D organic nanosheets (2DONs) with high mobility have received tremendous attention due to thickness of few molecular layers. However, ultrathin 2DONs with high luminescence efficiency and flexibility simultaneously are rarely reported. Here, the ultrathin 2DONs (thickness: 19 nm) through the modulation of tighter molecular packing (distance: ≈3.31 Å) achievable from the incorporation of methoxyl and dipenylamine (DPA) groups into 3D spirofluorenexanthene (SFX) building blocks is successfully prepared. Even with closer molecular stacking, ultrathin 2DONs still enable the suppression of aggregation quenching to exhibit higher quantum yields of blue emission (ΦF  = 48%) than that on amorphous film (ΦF  = 20%), and show amplified spontaneous emission (ASE) with a mediate threshold (332 mW cm-2 ). Further, through drop-casting method, the ultrathin 2DONs are self-organized into large-scale flexible 2DONs films (1.5 × 1.5 cm) with the low hardness (H: 0.008 Gpa) and low Young's modulus (Er : 0.63 Gpa). Impressively, the large-scale 2DONs film can realize electroluminescence performances with a maximum luminance (445 cd m-2 ) and low turn on voltage (3.7 V). These ultrathin 2DONs provide a new avenue for the realization of flexible electrically pumping lasers and intelligent quantum tunneling systems.

In Situ Super-Hindrance-Triggered Multilayer Cracks for Random Lasing in π-Functional Nanopolymer Films.

In situ self-assembly of semiconducting emitters into multilayer cracks is a significant solution-processing method to fabricate organic high-Q lasers. However, it is still difficult to realize from conventional conjugated polymers. Herein, we create the molecular super-hindrance-etching technology, based on the π-functional nanopolymer PG-Cz, to modulate multilayer cracks applied in organic single-component random lasers. Massive interface cracks are formed by promoting interchain disentanglement with the super-steric hindrance effect of π-interrupted main chains, and multilayer morphologies with photonic-crystal-like ordering are also generated simultaneously during the drop-casting method. Meanwhile, the enhancement of quantum yields on micrometer-thick films (Φ = 40% to 50%) ensures high-efficient and ultrastable deep-blue emission. Furthermore, a deep-blue random lasing is achieved with narrow linewidths ~0.08 nm and high-quality factors Q ≈ 5,500 to 6,200. These findings will offer promising pathways of organic π-nanopolymers for the simplification of solution processes applied in lasing devices and wearable photonics.

Tetrachromatic vision-inspired neuromorphic sensors with ultraweak ultraviolet detection.

Sensing and recognizing invisible ultraviolet (UV) light is vital for exploiting advanced artificial visual perception system. However, due to the uncertainty of the natural environment, the UV signal is very hard to be detected and perceived. Here, inspired by the tetrachromatic visual system, we report a controllable UV-ultrasensitive neuromorphic vision sensor (NeuVS) that uses organic phototransistors (OPTs) as the working unit to integrate sensing, memory and processing functions. Benefiting from asymmetric molecular structure and unique UV absorption of the active layer, the as fabricated UV-ultrasensitive NeuVS can detect 370 nm UV-light with the illumination intensity as low as 31 nW cm-2, exhibiting one of the best optical figures of merit in UV-sensitive neuromorphic vision sensors. Furthermore, the NeuVS array exbibits good image sensing and memorization capability due to its ultrasensitive optical detection and large density of charge trapping states. In addition, the wavelength-selective response and multi-level optical memory properties are utilized to construct an artificial neural network for extract and identify the invisible UV information. The NeuVS array can perform static and dynamic image recognition from the original color image by filtering red, green and blue noise, and significantly improve the recognition accuracy from 46 to 90%.

Pseudo-transistors for emerging neuromorphic electronics.

Artificial synaptic devices are the cornerstone of neuromorphic electronics. The development of new artificial synaptic devices and the simulation of biological synaptic computational functions are important tasks in the field of neuromorphic electronics. Although two-terminal memristors and three-terminal synaptic transistors have exhibited significant capabilities in the artificial synapse, more stable devices and simpler integration are needed in practical applications. Combining the configuration advantages of memristors and transistors, a novel pseudo-transistor is proposed. Here, recent advances in the development of pseudo-transistor-based neuromorphic electronics in recent years are reviewed. The working mechanisms, device structures and materials of three typical pseudo-transistors, including tunneling random access memory (TRAM), memflash and memtransistor, are comprehensively discussed. Finally, the future development and challenges in this field are emphasized.

A BN-Doped U-Shaped Heteroacene as a Molecular Floating Gate for Ambipolar Charge Trapping Memory.

Two wide-band gap U-shaped polycyclic aromatic hydrocarbons with/without boron and nitrogen (BN-) doping (BN-1 and C-1) were synthesized to tune the electronic features to suit the performance requirements for organic field-effect transistor memory (OFET-NVM). The chemical structures were characterized by scanning tunneling microscopy and single-crystal diffraction. Owing to the electron-donor effect of N and the high electron affinity of B, the BN-1-based OFET-NVM displays large ambipolar memory windows and an enhanced charge storage density compared to C-1 and most reported small molecules. A novel supramolecular system formed from BN-1 and PMMA contributes to fabricating uniform films with homogeneous microstructures, which serve as a two-in-one tunnelling dielectric and charge-trapping layer to realize long-term charge retention and reliable endurance. Our results demonstrate that both BN doping and supramolecular engineering are crucial for the charge trapping of OFET-NVM.

Engineering the First Coordination Shell of Single Zn Atoms via Molecular Design Strategy toward High-Performance Sodium-Ion Hybrid Capacitors.

Atomically dispersed Zn moieties are efficient active sites for accelerating the electrode kinetics of carbons for sodium-ion hybrid capacitors (SIHCs), but the low utilization and symmetric configuration of Zn single-atom greatly hamper the Na ion storage capability. Herein, a molecular design strategy is employed to synthesize high-density Zn single atoms with asymmetric Zn-N3 S coordination embedded in nitrogen/sulfur codoped carbon (Zn-N3 S-NSC). The key to this strategy lies in the Zn power-catalyzed condensation of trithiocyanuric acid molecules to generate S-doped g-C3 N4 , which can in situ coordinate with Zn sources to form Zn-N3 S moieties during pyrolysis. By virtue of the highly exposed Zn-N3 S moieties, Zn-N3 S-NSC presents ultrahigh reactivity, efficient electron transfer, and decreased ion diffusion barriers for SIHCs, rendering an impressive energy density of 215 Wh kg-1 and a maximum power density of 15625 W kg-1 . Moreover, the pouch cell displays a high capacity of 279 mAh g-1 after 4000 cycles. This work provides a new avenue for the regulation of the coordination configuration of single metal atoms in carbons toward high-performance electrochemical energy technologies at the molecular level.

A Reconfigurable Optoelectronic Synaptic Transistor with Stable Zr-CsPbI3 Nanocrystals for Visuomorphic Computing.

Reconfigurable phototransistor memory attracts considerable attention for adaptive visuomorphic computing, with highly efficient sensing, memory, and processing functions integrated onto a single device. However, developing reconfigurable phototransistor memory remains a challenge due to the lack of an all-optically controlled transition between short-term plasticity (STP) and long-term plasticity (LTP). Herein, an air-stable Zr-CsPbI3 perovskite nanocrystal (PNC)-based phototransistor memory is designed, which is capable of broadband photoresponses. Benefitting from the different electron capture ability of Zr-CsPbI3 PNCs to 650 and 405 nm light, an artificial synapse and non-volatile memory can be created on-demand and quickly reconfigured within a single device for specific purposes. Owing to the optically reconfigurable and wavelength-aware operation between STP and LTP modes, the integrated blue feature extraction and target recognition can be demonstrated in a homogeneous neuromorphic vision sensor array. This work suggests a new way in developing perovskite optoelectronic transistors for highly efficient in-sensor computing.

Enhanced Efficiency of Exciplex Emission from a 9-Phenylfluorene Derivative.

The exciplex-thermally activated delayed fluorescence (exciplex-TADF) system is an excellent candidate for the fabrication of high-efficiency organic light-emitting diodes (OLEDs) because of its more easily achieved small singlet-triplet energy splitting (ΔEST) and doping control. However, exciplex-TADF is still faced with the problems of low external quantum efficiency (ηext) and unclear effect of structure modification in electron acceptors. Herein, we provide a steric hindrance increase strategy to obtain high-efficiency exciplex emissions. Through introducing a 9-phenylfluorene group into N-ethylcarbazole of the dicyano-substituted 9-phenylfluorene, an electron acceptor material with increased steric hindrance is obtained, which helps the exciplex harvest a larger driving force and higher emission efficiencies. Encouragingly, the obtained OLED displays a maximum ηext of 25.8%, which is one of the best efficiency values among reported exciplex-OLEDs, simultaneously possessing excellent current efficiency of 83.6 cd A-1 and power efficiency of 93.7 lm W-1. It is expected that this work will offer a new avenue for designing electron acceptors for highly efficient exciplex emissions.