Sulfur Lone Pairs Open Avenues for π* → n Orange-to-Red TADF and OLEDs.

It is always important and fascinating to explore new organic emitters that exploit unconventional pathways to unveil their emission with unique properties, such as thermally activated delayed fluorescence (TADF). In this study, we report that the rarely explored sulfur lone pair (n) is a promising alternative, where the correlated π* → n emission can be used to attain strong TADF and thus practical OLEDs. The designed strategy incorporates several key concepts (Figure 1a), in which the persulfide aromatic spirocycle enhances spin-orbit coupling, thereby increasing the intersystem crossing rate.

Distinct Promotion of PEC Water Oxidation of TaO/α-FeO/Co-Ni PBA via Coupling Ni 3d with O 2p.

The development of robust and effective photoanodes is crucial for photoelectrochemical hydrogen production via total water splitting. Herein, the TaO/α-FeO/Co-Ni PBA (TFPB-1) photoanode was constructed by the compositing n-type TaO and n-type α-FeO followed by the deposition of p-type Co-Ni PBA. The IPCE of TFPB-1 was increased to 35.

Cross-Circulation Thrombectomy for Acute Middle Cerebral Artery Occlusion from Dislodged Thrombus of a Giant Internal Carotid Aneurysm: A Case Report.

Objective: Giant aneurysms of the cavernous segment of the internal carotid artery presenting as acute ischemic stroke (AIS) are rare and often misdiagnosed. Limited treatment experience further complicates management.

Case Presentation: A 70-year-old female presented with acute right middle cerebral artery (MCA) occlusion due to a dislodged thrombus from a giant internal carotid aneurysm.

Effective Improvement of Thermodynamics and Kinetics of BiVO Photoanode via CuI for Photoelectrochemical Water Oxidation.

The preparation of durable and efficient photoanodes for photoelectrochemical water oxidation is of great importance in promoting the development of green hydrogen production and artificial photosynthesis. Here, n-type BiVO was combined with p-type CuI to construct a CuI/BiVO (CIB-1) p-n heterojunction photoanode. The composite photoanode effectively overcame the drawbacks of BiVO, such as low separation and injection efficiency of photogenerated electron-hole pairs.

An imidazole-copper(I) metallacycle complex exhibiting thermochromic fluorescence.

In this paper, we firstly report the synthesis and structural characterization of a discrete coordination metallacycle complex, [CuI (bipy)] (1). The x-ray diffraction structure, temperature-dependent electronic absorption, and photoluminescence spectra have been investigated. The solid-state fluorescence at variable temperatures shows that complex 1 exhibits an obvious thermochromic fluorescence.

Single-Luminophore Molecular Engineering for Rapidly Phototunable Solid-State Luminescence.

Smart materials enabling emission intensity or wavelength tuning by light stimulus have attracted attention in cutting-edge fields. However, due to the general limitation of the dense molecular stacking (in solid states, especially in crystals) on photoresponsivity, constructing rapidly phototunable solid-state luminescent systems remains challenging. Herein, we present a new luminophore that serves as both a photoresponsive and a luminous group with enhanced conformational freedom to attain this goal, namely, relying on photoexcitation-induced molecular conformational change of an ionized persulfurated arene based on weak intermolecular aliphatic C-H⋅⋅⋅π interaction.

Achieving Dual Emission of Fluorescence and Phosphorescence from Anti-Kasha's Metal-Organic Halides for Information Encryption.

Luminescent materials typically emit their fluorescence or phosphorescence at a specific wavelength with different excitation energies via the so-called Kasha's rule. If fluorescence or phosphorescence emission via anti-Kasha's rule could be achieved, it will hold great promise for applications in many fields. In this work, we report the synthesis and characterization of new metal-organic halide materials with dual emission of efficient room-temperature phosphorescence and fluorescence, which obey anti-Kasha's rule.

Efficient purging of deleterious mutations contributes to the survival of a rare conifer.

Cupressaceae is a conifer family rich in plants of horticultural importance, including , , , and , yet genomic surveys are lacking for this family. , one of the many rare conifers that are threatened by climate change and anthropogenic habitat fragmentation, plays an ever-increasing role in ecotourism in Tibet. To infer how past climate change has shaped the population evolution of this species, we generated a chromosome-scale genome (10.

Suppressing the Thermal Quenching Effect via a Cluster Conformer in Copper(I)-Iodide Coordination Polymeric Phosphors for High-Power White LED Lighting.

High-power LED lighting is a crucial challenge due to the notorious thermal quenching (TQ) effect of traditional phosphors at high operating currents, which would result in poor device performance and hamper practical optoelectronic application. Herein, we demonstrate ligand engineering of a cubane- versus staircase-like [CuI] conformer as a node in coordination polymers, which remarkably suppresses the TQ effect of cluster-based photoluminescence. For complex (the formula [CuI(bbimb)]) with the cubane-like [CuI] conformer as a node, the metallophilicity interaction enables ultrabright triplet emission with a photoluminescence quantum yield over 82%, and the phonon-assisted detrapping process of excitons effectively suppresses the TQ effect in the wide temperature range.

π-Sticked Metal‒Organic Monolayers for Single-Metal-Site Dependent CO Photoreduction and Hydrogen Evolution Reaction.

Hierarchical self-assembly of 2D metal‒organic layers (MOLs) for the construction of advanced functional materials have witnessed considerable interest, due to the increasing atomic utilizations and well-defined atom‒property relationship. However, the construction of atomically precise MOLs with mono-/few-layered thickness through hierarchical self-assembly process remains a challenge, mostly because the elaborate long-range order is difficult to control via conventional noncovalent interaction. Herein, a quadruple π-sticked metal‒organic layer (πMOL) is reported with checkerboard-like lattice in ≈1.

Drug-drug interaction prediction based on local substructure features and their complements.

The properties of drugs may undergo changes when multiple drugs are co-administered to treat co-existing or complex diseases, potentially leading to unforeseen drug-drug interactions (DDIs). Therefore, predicting potential drug-drug interactions has been an important task in pharmaceutical research. However, the following challenges remain: (1) existing methods do not work very well in cold-start scenarios, and (2) the interpretability of existing methods is not satisfactory.

Spin Manipulation in a Metal-Organic Layer through Mechanical Exfoliation for Highly Selective CO Photoreduction.

Spin manipulation of transition-metal catalysts has great potential in mimicking enzyme electronic structures to improve activity and/or selectivity. However, it remains a great challenge to manipulate room-temperature spin state of catalytic centers. Herein, we report a mechanical exfoliation strategy to in situ induce partial spin crossover from high-spin (s=5/2) to low-spin (s=1/2) of the ferric center.

Multicomponent Anti-Kasha's Rule Emission from Nanotubular Metal-Organic Frameworks for Selective Detection of Small Molecules.

The peak photoluminescence (PL) of conventional fluorophores is independent of the excitation wavelength (called Kasha's rule), while the search of metal-organic framework materials with the so-called anti-Kasha's rule emission remains very limited. Herein, we report the observation of anti-Kasha's rule emission in a multicomponent PL three-dimensional nanotubular metal-organic framework ( ), [Zn(μ-L)(μ-bix)]·0.33HO [HL = biphenyl-3,5-dicarboxylic acid; bix = 1,4-bis(imidazole-1-ylmethyl)benzene].

High-temperature negative thermal quenching phosphors from molecular-based materials.

High-temperature negative thermal quenching (NTQ) phosphors are crucial to high-performance light-emitting devices. Herein, we report the high-temperature NTQ effect in deep-red to near-infrared (NIR) emitting copper iodide cluster-based coordination polymers as unconventional phosphors, whose NTQ operating temperature can reach as high as 500 K, the highest temperature reached by NTQ molecular-based materials.

A Copper Iodide Cluster-Based Coordination Polymer as an Unconventional Zero-Thermal-Quenching Phosphor.

Phosphor-converted white light-emitting diodes (pc-wLEDs) are promising candidates for next-generation solid-state lighting and display technologies. However, most of the conventional phosphors in pc-wLED devices suffer from serious thermal quenching (TQ) at high temperatures. Herein, we investigate an unconventional high-efficiency metal-halide cluster-based phosphor with dynamic Cu-Cu interactions that can resist the TQ effect of photoluminescence.

High-contrast reversible multiple color-tunable solid luminescent ionic polymers for dynamic multilevel anti-counterfeiting.

Dynamic color-tunable luminescent materials, which possess huge potential applications in advanced multilevel luminescence anti-counterfeiting, are of considerable interest. However, it remains challenging to develop simple high-contrast reversible multiple (triple or more than triple) color-tunable high-efficiency solid luminescent materials with low cost, facile synthesis, and good processability. Herein, by simply grafting charged multi-color AIEgen-based chromophores into polymers, a series of high-efficiency multiple color-tunable luminescent single ionic polymers are constructed through tuning feed ratios, counter anions and reaction solvents.

Roles of Bromodomain Extra Terminal Proteins in Metabolic Signaling and Diseases.

BET proteins, which recognize and bind to acetylated histones, play a key role in transcriptional regulation. The development of chemical BET inhibitors in 2010 greatly facilitated the study of these proteins. BETs play crucial roles in cancer, inflammation, heart failure, and fibrosis.

A Red-Emitting Cu(I)-Halide Cluster Phosphor with Near-Unity Photoluminescence Efficiency for High-Power wLED Applications.

Solid-state lighting technology, where light-emitting diodes (LEDs) are used for energy conversion from electricity to light, is considered a next-generation lighting technology. One of the significant challenges in the field is the synthesis of high-efficiency phosphors for designing phosphor-converted white LEDs under high flux operating currents. Here, we reported the synthesis, structure, and photophysical properties of a tetranuclear Cu(I)-halide cluster phosphor, (bppm = bisdiphenylphosphinemethane), for the fabrication of high-performance white LEDs.

Seeing through the hedge: Phylogenomics of Thuja (Cupressaceae) reveals prominent incomplete lineage sorting and ancient introgression for Tertiary relict flora.

The Eastern Asia (EA) - North America (NA) disjunction is a well-known biogeographic pattern of the Tertiary relict flora; however, few studies have investigated the evolutionary history of this disjunction using a phylogenomic approach. Here, we used 2369 single copy nuclear genes and nearly full plastomes to reconstruct the evolutionary history of the small Tertiary relict genus Thuja, which consists of five disjunctly distributed species. The nuclear species tree strongly supported an EA clade Thuja standishii-Thuja sutchuenensis and a "disjunct clade", where western NA species T.

Negative/Zero Thermal Quenching of Luminescence Electronic Structural Transition in Copper-Iodide Cluster-Based Coordination Networks.

Photoluminescence (PL) intensity in organic or metal-organic emitters usually suffers from thermal quenching (TQ), which severely hinders their industrial applications. The development of negative thermal quenching (NTQ) and/or zero thermal quenching (ZTQ) materials depends on a better understanding of the mechanisms underpinning TQ in luminescent solids. In this work, we investigated the temperature dependence of thermally activated delayed fluorescence (TADF) in copper(I)-organic coordination polymers (CP) ligated with an imidazole or triazole derivative over a broad temperature range.

Controlling dynamic magnetic properties of coordination clusters via switchable electronic configuration.

Large-sized coordination clusters have emerged as a new class of molecular materials in which many metal atoms and organic ligands are integrated to synergize their properties. As dynamic magnetic materials, such a combination of multiple components functioning as responsive units has many advantages over monometallic systems due to the synergy between constituent components. Understanding the nature of dynamic magnetism at an atomic level is crucial for realizing the desired properties, designing responsive molecular nanomagnets, and ultimately unlocking the full potential of these nanomagnets for practical applications.

Characteristics and prognosis of acute basilar artery occlusion in minor to moderate stroke and severe stroke after endovascular treatment: A multicenter retrospective study.

Objective: We aimed to investigate characteristics and outcomes of patients receiving mechanical thrombectomy (MT) between minor to moderate stroke and severe stroke caused by acute basilar artery occlusion (BAO).

Methods: We retrospectively reviewed the data of all patients with BAO who underwent MT from three stroke centers between January 2016 and January 2020. The patients were dichotomized as minor to moderate or severe stroke group according to their admission National Institutes of Health Stroke Scale (NIHSS) score <21and ≥21.

Ionothermal synthesis of octahedral lanthanoid coordination networks exhibiting slow magnetization relaxation and efficient photoluminescence.

An ionothermal reaction of lanthanoid salts with tetraethyl-p-xylenediphosphonate (tepxdp) in ionic liquids, such as choline chloride and malonic acid, resulted in the formation of three novel lanthanoid-organic coordination networks with the formula [Ln(H2pxdp)1.5]n {Ln = Tb (1), Dy (2) and Ho(3) and H4pxdp = p-xylenediphosphonic acid}. The structures, photoluminescence and magnetic properties of the three compounds were investigated in detail.

Azo-Label Heterometal-Organic Rhomboids Exhibiting Photoswitchable NIR Luminescence in Crystalline State.

Photochromism is an important strategy for realizing reversible light-controllable fluorescence switching. In spite of several reports on fluorescence switching via a photochromic process, the success of photochromic multimetallic complexes reversibly showing fluorescence switching in the solid or crystalline state has been limited for their application importance. Here, we report a photoswitchable near-infrared (NIR) fluorescence based on photochromism in the azo-label 3d/4f heterometal-organic rhomboids, (Ln = Eu (), Yb (), and Er ()), in the crystalline state.