Encapsulation of metal clusters in porous organic cages (POCs) is a promising strategy for metalloenzyme-mimetic catalysts. However, constructing POCs with endogenous metal clusters and achieving atomic-level control over their formation and structural evolution remains a key challenge. Here, we realize the in situ growth of a cubic tetranuclear Ag-halide cluster in an imine-based [4+6] POC (α-Ag4X4@Cage-2, X = Cl, Br, I) via coordination-driven tandem assembly, monitored by time-resolved mass spectrometry. Upon heating, α-Ag4X4@Cage-2 (X = Cl, Br) undergoes a single-crystal-to-single-crystal transformation, with symmetry breaking via Ag-X bond cleavage and structural transition from cubane to distorted hexahedron (β phase). This is a rare atomic-level observation of thermally induced structural change of endogenous metal clusters in molecular cages. For CO2 electroreduction, β-Ag4X4@Cage-2 reaches 98.7% FECO at -1.05 V versus RHE with 100 h stability (outperforming its α-phase counterpart), a TOF of 100 060 h-1 at 500 mA cm-2, ranking among top molecular materials. Mechanistic studies reveal that the β-Ag4X4 structural distortion disrupts charge symmetry of the four Ag atoms and localizes electrons at the bond-cleaved Ag site, lowering the energy barrier for key *COOH intermediate formation. This work offers insights into the dynamic evolution of confined metal clusters via precise host-guest structural engineering.

This article reports on the anti-cancer properties of a series of binuclear gold(I) complexes containing mixed bis(diphenylphosphine)carborane and bis(N-heterocyclic carbene) bridging ligands. Among them, the most active complex, 1b, is stable to serum thiols (such as glutathione and serum albumin), exhibits cytotoxicity against cancer cells, inhibits thioredoxin reductase activity, and effectively suppresses tumor growth in two mouse models. Complex 1b was also found to inhibit angiogenesis in cell culture and tumor models. We used unbiased thermal proteosome profiling to identify the molecular targets of 1b. The results showed that the ubiquitin-conjugating enzyme E2 C UBE2C, an oncogenic protein highly expressed in a number of cancers, interacts with 1b, and this result was further validated by cellular thermal shift assays and biolayer interferometry assays.

Skeletal editing of aza-heteroarenes has become a powerful strategy for late-stage molecular diversification in medicinal and material chemistry. π-Conjugated azaborines have attracted increasing attention due to their exceptional optoelectronic properties and practical applications in organic light-emitting diodes (OLEDs). However, ring manipulation of boron-containing rings remains a long-standing challenge, and cascade skeletal editing beyond monocyclic frameworks is largely underdeveloped. Here, we report a boron-deleting annulation (BDA) reaction that enables the transformation of unstrained bicyclic 1,4-azaborines into a diaza-pentagon-heptagon pair in a one-pot reaction, affording a wide array of nonalternant π-conjugated azaborines (>35 examples) with unique optoelectronic properties. This late-stage modification approach thus balances synthetic simplicity with structural diversity and expands the accessible chemical space of functional π-systems for optoelectronic applications. Additionally, the BDA product can trigger consecutive cyclodehydrogenation to zipping-up sophisticated nanographenes via further periphery-to-core extension. Mechanistic studies reveal a series of unprecedented ring contraction-expansion processes. Remarkably, yellow OLEDs based on BDA product achieved a record 23.0% external quantum efficiency without delayed fluorescence, demonstrating the potential for high-performance electroluminescence.

ABSTRACT Bispecific antibodies (BsAbs) represent a growing class of cancer immunotherapeutics, yet their wider adoption remains limited by complex recombinant production and limited manufacturing efficiency. Here, we report a chemically assembled macrophage‐engaging glypican‐3 × signal regulatory protein‐α (SIRP‐α) bispecific antibody for the treatment of liver cancer. Using our bifunctional linker, glypican‐3‐binding peptide dimers were conjugated to a native anti‐SIRP‐α IgG via a rapid one‐pot, two‐step process, yielding a novel dendritic bispecific antibody (dBsAb). Such a construct simultaneously targets glypican‐3‐positive hepatocellular carcinoma cells and blocks the CD47–SIRP‐α axis, thereby promoting macrophage engagement and phagocytosis. In vitro studies showed substantially enhanced macrophage adhesion and tumor cell clearance compared with the monoclonal antibody. In an in vivo experiment, dBsAb demonstrated a 68% reduction in tumor growth, with increased macrophage infiltration, M1 polarization, and elevated antigen presentation without observable systemic toxicity. This chemical assembly approach offers a practical alternative to recombinant methods for constructing bispecific antibodies and may facilitate the development of macrophage‐directed immunotherapies.

Ginseng is widely praised for its benefits on cancer patients, often attributed to its metabolite compound K (CK). Here, we synthesized a derivative (CKD-4) that, compared with CK, exhibited enhanced cellular uptake, threefold greater cytotoxicity, and improved pharmacokinetics. CKD-4 induced significant growth inhibition on lung cancer patient-derived organoids, and on cell line-derived xenografts with minimal systemic toxicity. CKD-4 also suppressed orthotopic lung tumor growth in immunocompetent mice with enhanced antitumor immune infiltration. Using proteome integral solubility alteration and ProTargetMiner analyses, the mitochondrial phospholipid transfer protein PRELID3B was unbiasedly identified as a shared anticancer target of CK and CKD-4. PRELID3B is a potential pancancer therapeutic target and prognostic biomarker supported by cancer genetics and transcriptomics evidence. Both CK and CKD-4 stabilize PRELID3B in cellular thermal shift assay and bind PRELID3B with Kd of 23 µM and 5 µM, respectively, measured by biolayer interferometry. Multiomics analyses revealed that CK and CKD-4 share similar anticancer mechanisms, involving mitochondrial phospholipid depletion, integrated stress response activation, and immunomodulatory pathways induction associated with PRELID3B inhibition. This study provides the basis for the immunomodulatory and anticancer effects of ginseng metabolites through targeting PRELID3B, and illustrates the application of orthogonal proteomics in target identification of natural compounds.

The origin of biological chirality remains a fundamental scientific mystery. Developing artificial systems with on‐off responsive chiral induction and transfer, and elucidating their mechanisms, is of paramount importance. Here, we report the first pair of chiral porous organic cage ( R/S ‐ BA‐PAC ) exhibiting unprecedented chiral afterglow in a film state, boosting a remarkable lifetime of 1.2 s and a dissymmetry factor ( g lum ) of 0.001. Loading rhodamine B (RB) guest molecules enables multicolor afterglow ranging from green to red, achieving 88% energy transfer. Notably, the confined RB displays a pronounced mirror‐imaged circular dichroism signal, and the induced chirality of RB demonstrates completely reversible on‐off switching under water vapor/thermal stimulation, which is extremely rare in covalent porous materials. Experimental and theoretical studies have shown that the distortion of the benzoic acid moiety in RB is caused by hydrogen‐bonding interactions between benzoic acid group and the BA‐PAC . This distortion disrupts the electric‐magnetic dipole moment orthogonality of RB, inducing its chirality. Furthermore, the reversible disruption and reconstruction of the host–guest hydrogen‐bonding network induced by external stimuli is a key mechanism for dynamic chiral transfer. This study bridges chiral induction and stimuli response in porous cages, providing a versatile biomimetic platform for investigating molecular‐level dynamic chirality transfer.

This article reports on the anti-cancer properties of a series of binuclear gold(I) complexes containing mixed bis(diphenylphosphine)carborane and bis(N-heterocyclic carbene) bridging ligands. Among them, the most active complex, 1b, is stable to serum thiols (such as glutathione and serum albumin), exhibits cytotoxicity against cancer cells, inhibits thioredoxin reductase activity, and effectively suppresses tumor growth in two mouse models. Complex 1b was also found to inhibit angiogenesis in cell culture and tumor models. We used unbiased thermal proteosome profiling to identify the molecular targets of 1b. The results showed that the ubiquitin-conjugating enzyme UBE2C, an oncogenic protein highly expressed in a number of cancers, interacts with 1b, and this result was further validated by cellular thermal shift assays and biolayer interferometry assays.

Flexible near-infrared (NIR) organic light-emitting diodes (OLEDs) face efficiency challenges due to low photoluminescence quantum yields (PLQYs) in NIR emitters, governed by the energy gap law. Accelerating radiative transitions via the Purcell effect in optical microcavities offers a solution, but conventional flexible semitransparent electrodes struggle to balance microcavity-enhanced PLQY and light outcoupling efficiency (OCE). We address this with a micro-structured magnesium-bismuth (Mg-Bi) alloy electrode offering 40% broadband transmittance (400-1600 nm) and conductivity (29.3 Ω ◻-1). The alloy's low real permittivity supports less confined surface plasmon polariton and, with a capping layer, yields 60% NIR transmittance in an organic-to-air optical configuration. This design achieves 42.3% OCE and elevates the PLQY of a 704 nm NIR emitter to 71.8%, enabling flexible NIR-OLEDs with a record 24.3% external quantum efficiency. The synergy of optical engineering and conductive microstructures establishes a universal strategy for high-efficiency flexible NIR optoelectronics.

ABSTRACT Luminescent d10 carbene‐metal‐amide (CMA) complexes are a promising class of thermally activated delayed fluorescence (TADF) organic light‐emitting diode (OLED) emitters. However, the principles for modifying ligands to maximize OLED efficiency and operational stability remain unclear. Here, we reveal the key role of metal (n+1)p‐nd orbital hybridization and excited‐state metal‐ligand π‐interactions in affecting the excited‐state stability and electro‐/photoluminescence efficiency of CMA emitters. Using density functional theory (DFT), high‐level coupled cluster singles and doubles (CCSD) method, and combined DFT and multireference configuration interaction (DFT/MRCI) calculations, we found that in the excited state, metal atoms and carbazole nitrogen atoms form π‐interactions, which is weakened by the weakening of metal (n+1)p‐nd orbital hybridization. The weakened metal–nitrogen (M─N) π‐interaction is conducive to more flexible rotation of the excited‐state dihedral angle, thereby increasing the radiative decay rate (kTADF). This rationalizes the general trend of kTADF for CMA emitters: Ag > Au > Cu. However, the weakening of the excited‐state M─N π‐interaction reduces the strength of the M─N bond and facilitates bond dissociation in the excited state, thereby impairing the stability of the emitter. Our calculations show that introducing electron‐withdrawing or π‐extended substituents on carbazole ligands reduces excited‐state M─N π‐interactions, thereby improving kTADF, but may impair emitter stability and device operational lifetime.

Recently, hidden self-assembly pathways have emerged as a powerful strategy to control supramolecular polymerization and access otherwise unachievable nanostructures. However, the use of hidden pathways to construct multicomponent supramolecular block copolymers (BCPs) with tailorable sequences remains underexplored. Herein, we report the synthesis of sequence-tailorable supramolecular BCPs by exploiting seed-activated hidden self-assembly pathways of three Ir(iii) complexes 1-3. At H2O/CH3CN = 83 : 17, all three complexes initially form kinetically trapped nanoparticles A. Upon aging, complexes 1 and 3 spontaneously evolve into long-lived nanospheres B, whereas complex 2 evolves into C-type fibrillar assemblies. Although C-type fibrillar assemblies of 1 and 3 were not obtained by unseeded self-assembly, the addition of 2C seeds activated their C-type growth, affording the seed-accessible species 1C and 3C. These species are regarded as kinetically persistent C-type assemblies rather than as the spontaneous thermodynamic products of 1 and 3 under the same conditions. Importantly, both 1C and 3C could further serve as initiators for seeded growth. Through sequential seeded supramolecular polymerization, all six three-component 5-block sequences were successfully obtained. The heterogeneous nucleation process was supported by time-dependent UV-vis absorption spectra, spectral superposition analysis, DLS, and TEM identification of segmented nanostructures. This study highlights the potential of seed-activated hidden self-assembly pathways for constructing multicomponent supramolecular BCPs with programmable sequences.

Although gold-TADF (thermally activated delayed fluorescence) emitters have attractive prospects as next-generation practical OLED emitters, the performance of OLEDs utilizing gold(I)- and gold(III)-TADF emitters lags behind the requirements of practical applications, and device lifetime has become a bottleneck. Here, novel pincer gold(III)-TADF emitters that are easily fabricated with tunable donor and acceptor ligands are presented. These pincer gold(III)-TADF emitters exhibit an extended molecular π-distance along the transition dipole moment, resulting in a significant reduction in the electron exchange energy between the S1 and T1 excited states, thus narrowing the singlet-triplet energy gap (ΔEST). The combination of small ΔEST and heavy-atom (Au, S) effect greatly enhances spin-flip dynamics and produces efficient TADF (photoluminescence quantum yields up to 90%) with high radiative decay rate constants (kr up to 106 s-1), and short lifetimes (τ less than 1.2 µs) in thin films at room temperature. Vacuum-deposited OLEDs based on these gold(III)-TADF emitters demonstrate impressive stability, achieving i) a high maximum external quantum efficiency (EQEmax) of up to 22.2%, and ii) a record- long operational lifetime (LT95) of 3831 h at an initial luminance of 1000 cd m-2. This excellent durability makes the pincer gold(III)-TADF emitter a promising and competitive alternative to iridium and platinum emitters for practical OLED applications.

The utilization of phosphorescent metal complexes as emissive dopants for organic light-emitting diodes (OLEDs) has been the subject of intense research. Cyclometalated Pt(II) complexes are particularly popular triplet emitters due to their color-tunable emissions. To make them viable for practical applications as OLED emitters, it is essential to develop Pt(II) complexes with high radiative decay rate constants (k(r)) and photoluminescence quantum yields (PLQY). To this end, an efficient and accurate prediction tool is highly desirable. In this work, we propose a general yet powerful protocol achieving metal complex generation, high throughput virtual screening (HTVS), and fast predictions with high accuracy. More than 3600 potential structures are generated in a synthesis-friendly manner. Moreover, three HTVS-machine learning (ML) models are established using different algorithms with carefully designed features that are suitable for metal complexes. Specifically, 30 potential candidates are filtered out by HTVS-ML models with a three-tier screening rule and put into accurate predictions with experimental calibration Delta-learning method. The highly accurate prediction approach further reduces the stress of experiments and inspires greater confidence in identifying the most promising complexes as excellent emitters. As a result, 12 promising complexes (k(r) > 10(5) s(-1) and PLQY > 0.6) with the same superior core structures are confirmed from over 3600 Pt-complexes. Experiments revealed that two very close complexes have excellent emission properties and are consistent with the prediction results, providing strong evidence for the efficacy of the proposed protocol. We expect this protocol will become a valuable tool, expediting the rational design and rapid development of novel OLED materials with desired properties.

Copper-based organic light-emitting diodes (OLEDs) are low-cost alternatives to precious metal-based OLEDs, but currently no such OLEDs can meet the practical requirements for high colour purity, device efficiency, and operational stability. Carbene-Cu(I)-amide emitters reported here exhibited thermally activated delayed fluorescent emission with quantum efficiencies up to 0.90 and radiative decay rates of 2.7 × 106 s-1. These enable blue to near-infrared Cu(I)-OLEDs with high brightness (265,000 cd m-2) and extended LT95 lifetime (3582 hours at 1000 cd m-2). Deuteriation and π-extension of carbazole significantly enhance OLED stability. Cu(I)-sensitized fluorescence OLEDs showed efficient narrowband electroluminescence (λmax 612-614 nm; full-width half maximum of 33-38 nm; maximum external quantum efficiencies reach 21.9%) and prolonged LT95 lifetime (up to 3689 h at 1000 cd m-2). This work highlights earth-abundant metal-based sensitized-OLEDs that exhibit high colour purity and long device lifetime comparable to the best non-iridium metal-based OLEDs.

A highly efficient, iron(III)-BPsalan complex-catalyzed asymmetric 1,3-dipolar cycloaddition of nitrones and α,β-unsaturated acyl imidazoles has been developed to afford isoxazolidine (31 examples) and isoxazoline derivatives (13 examples) in moderate to excellent yields (up to 99%) and excellent stereoselectivity (up to 99% ee and >20:1 dr). The reaction proceeds readily in acetone under air conditions, maintaining high efficiency and selectivity.

Platinum-based chemotherapy drugs play an indispensable role in clinical cancer treatment, but exhibit considerable side effects due to their non-specific mechanism of killing cancer cells and normal cells. In this regard, the use of antibodies conjugated to anti-cancer platinum complexes will enable better differentiation of cancer cells from normal cells. Here, six pincer-platinum(II) NHC (N-heterocyclic carbene) complexes are reported, one of which has an amino group on the N-alkyl group of the NHC ligand. This platinum(II) complex is used as the payload for platinum(II)-based antibody-drug conjugate (ADC) targeting human epidermal growth factor receptor 2 (HER-2). Notably, this ADC can specifically bind to the HER-2 antigen, distinguish target cells from non-target cells, and exhibit good anti-tumor activity in vitro and in vivo.

AbstractColor‐tunable white organic light‐emitting diodes (CT‐WOLEDs) have attracted widespread attention given their large color variation to meet the different daily scenarios from the perspective of circadian rhythm. However, most reported CT‐WOLEDs, especially the tri‐color devices, exhibit poor performances and sophisticated structures. Here, a simple structure tri‐color CT‐WOLED is demonstrated that simultaneously exhibits high efficiency, ultralong operation lifetime, and wide color‐tunable range for dynamic sunlight emulation. The design is based on a newly developed platinum complex that can emit light efficiently in both monomer and aggregation states, providing voltage‐dependent green‐to‐red phosphorescence emission, not only ensuring tunable colors in WOLEDs but also simplifying the device structure. Combining with a blue delayed fluorescence material, this hybrid device exhibits a wide range of tunable colors with Commission Internationale de l’Eclairage 1931 (CIE) coordinates and correlated color emperature (CCT) shifts from (0.502, 0.474) and 2628 K at 2.6 V to (0.211, 0.334) and 14860 K at 8 V, achieving good visual alignment with sunlight color throughout the day. This same device also shows high external quantum efficiencies from 28.8% at maximum to 26.2% at 5000 cd m−2. Furthermore, an impressively long time of 21,144 h is achieved to decay to 90% of the initial luminance at 100 cd m−2, being the longest among recorded CT‐WOLEDs.

Using C–H substrates as limiting reagents to achieve non-directed C–H activation with high selectivity has been a long-standing challenge in organic synthesis. Recently in Nature Catalysis, Liu et al. introduce a biomimetic catalytic system that employs Cu(II)-bound tert-butoxy radicals for site-selective C–H abstraction, enabling highly efficient asymmetric C(sp3)–H oxidation.

Selective functionalization of ubiquitous C-H bonds in organic molecules provides a straightforward and efficient approach to construct complex molecules with fewer synthetic steps and high atom economy, thus promoting more sustainable and economical chemical synthesis. A formidable challenge in the field is to increase the turnover numbers (TONs) for catalytic C-H functionalization reactions reported in the literature (generally <10,000) to reasonably high levels to reduce the cost of the reaction. Another challenge is the selective functionalization of less reactive primary C(sp3)-H bonds compared to other types of more reactive C-H bonds. We now demonstrate an efficient iridium porphyrin-catalysed asymmetric carbene insertion into primary N-adjacent C(sp3)-H bond of N-methyl indoline and N-methyl aniline derivatives. Using chiral iridium porphyrin as a catalyst, chiral β-amino acid derivatives have been obtained with very high yields and excellent ee values (up to 99%), and TONs as high as 84,000 to 1,380,000. The reaction can be readily performed on a 100 g scale while retaining its high efficiency and selectivity. We also show that this iridium catalysis can efficiently access oligomers and polymers of β-amino acid derivatives via stepwise C-H insertion, demonstrating its potential applications in materials science via C-H bond functionalization reactions.

Helical molecular carbons (HMCs) possess high absorption/luminescence dissymmetry factors (gabs/glum) and significant luminescence quantum yield (Φlum), resulting in a high circularly polarized luminescence (CPL) brightness (BCPL), which is essential for the development of CPL materials for practical applications. Herein, we designed and synthesized a series of boron‐nitrogen (BN)‐doped HMCs, named π‐extended heli(aminoborane)s (E[10]HAB‐A, E[10]HAB‐B and E[10]HAB‐C), consisting of laterally π‐extended [10]helicene skeleton with alternating N and B atoms at the inner rim. The aromaticity, electronic structures, and photophysical properties of E[10]HAB‐A/B/C were systematically investigated through experiments and theoretical calculations. E[10]HAB‐A/B/C displayed remarkable photophysical properties, including high molar extinction coefficient and bright narrowband emission. The isolated enantiomers of E[10]HAB‐A/B/C exhibited intense circular dichroism (CD) and CPL, in which E[10]HAB‐A shows gabs and glum values up to 0.024 and 0.017, simultaneously with high Φlum of 82% and a narrow full width at half maximum of 16 nm. Accordingly, E[10]HAB‐A exhibits a BCPL as high as 583 M−1 cm−1, which is the largest value among the reported BN‐doped HMCs. Our study indicates that inner rim BN‐doping and π‐extension are effective strategies to achieve high Φlum and balanced glum values in HMCs.