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Host‐guest chemistry, a pivotal branch of supramolecular chemistry, plays an essential role in understanding and constructing complex structures through non‐covalent interactions. Organic molecular cages, characterized by their intrinsic confined cavities, can selectively bind a variety of guest molecules. Their host–guest chemistry has been well studied in the solution phase, and several attempts have been made to encode well‐defined molecular architectures into solid‐state polymeric materials. However, only limited studies have explored their potential in the solid state, where their lack of robustness and less ordered networks significantly hinder practical applications. Herein, we report the synthesis of a single‐crystal cage framework and a systematic study of its host–guest chemistry, spanning from the solution state to the solid state. Our studies reveal that the host–guest interactions inherent to the cage are successfully maintained in the solid‐state polymeric material. Furthermore, the framework's robustness allows for the guest molecules (fullerene) to be released triggered by an organic acid (trifluoroacetic acid), with subsequent regeneration of the framework through an organic base (triethylamine) treatment. Our findings represent the first synthesis of a robust, single‐crystal cage framework exhibiting highly selective and reversible host–guest chemistry, thus showing great potential towards molecular separation application. [ABSTRACT FROM AUTHOR]

Due to the challenge of cleaving O−O bonds at single Co sites, mononuclear Co complexes typically show poor selectivity for the four‐electron (4e−) oxygen reduction reaction (ORR). Herein, we report on selective 4e− ORR catalyzed by a Co porphyrin with a hanged ZnII ion. Inspired by Cu/Zn‐superoxide dismutase, we designed and synthesized 1‐CoZn with a hanging ZnII at the second sphere of a Co porphyrin. Complex 1‐CoZn is much more effective than its Zn‐lacking analogues to catalyze the 4e− ORR in neutral aqueous solutions, giving an electron number of 3.91 per O2 reduction. With spectroscopic studies, the hanging ZnII was demonstrated to be able to facilitate the electron transfer from CoII to O2, through an electronic "pull effect", to give CoIII‐superoxo. Theoretical studies further suggested that this "pull effect" plays crucial roles in assisting O−O bond cleavage. This work is significant to present a new strategy of hanging a ZnII to improve O2 activation and O−O bond cleavage. [ABSTRACT FROM AUTHOR]

Integrating controllable spin states into single‐molecule magnets (SMMs) enables precise manipulation of magnetic interactions at a molecular level, but remains a synthetic challenge. Herein, we developed a 3d–4f metallacrown (MC) magnet [DyNi5(quinha)5(Clsal)2(py)8](ClO4) ⋅ 4H2O (H2quinha=quinaldichydroxamic acid, HClsal=5‐chlorosalicylaldehyde) wherein a square planar NiII is stabilized by chemical stacking. Thioacetal modification was employed via post‐synthetic ligand substitutions and yielded [DyNi5(quinha)5(Clsaldt)2(py)8](ClO4) ⋅ 3H2O (HClsaldt=4‐chloro‐2‐(1,3‐dithiolan‐2‐yl)phenol). Thanks to the additional ligations of thioacetal onto the NiII site, coordination‐induced spin state switching (CISSS) took place with spin state altering from low‐spin S=0 to high‐spin S=1. The synergy of CISSS effect and magnetic interactions results in distinct energy splitting and magnetic dynamics. Magnetic studies indicate prominent enhancement of reversal barrier from 57 cm−1 to 423 cm−1, along with hysteresis opening and an over 200‐fold increment in coercive field at 2 K. Ab initio calculations provide deeper insights into the exchange models and rationalize the relaxation/tunnelling pathways. These results demonstrate here provide a fire‐new perspective in modulating the magnetization relaxation via the incorporation of controllable spin states and magnetic interactions facilitated by the CISSS approach. [ABSTRACT FROM AUTHOR]

Integrating aggregation‐induced emission (AIE) into thermally activated delayed fluorescence (TADF) emitters holds great promise for the advancement of highly efficient organic light emitting diodes (OLEDs). Despite recent advancements, a thorough comprehension of the underlying mechanisms remains imperative for the practical application of such materials. In this work, we introduce a novel approach aimed at modulating the TADF process by manipulating dynamic processes in excited states through aggregation effect. Our findings reveal that aggregation not only enhances both prompt and delayed fluorescence simultaneously but also imposes constraints on molecular reorientation. This constraint reinforces spin‐orbit coupling and reduces the energy gap between singlets and triplets. These insights deepen our understanding of the fundamental mechanisms governing the aggregation effect on TADF materials and provide valuable guidance for the design of high‐efficiency photoluminescent materials. [ABSTRACT FROM AUTHOR]

In aqueous aluminum‐ion batteries (AAIBs), the insertion/extraction chemistry of Al3+ often leads to poor kinetics, whereas the rapid diffusion kinetics of hydronium ions (H3O+) may offer the solution. However, the presence of considerable Al3+ in the electrolyte hinders the insertion reaction of H3O+. Herein, we report how oxygen‐deficient α‐MoO3 nanosheets unlock selective H3O+ insertion in a mild aluminum‐ion electrolyte. The abundant oxygen defects impede the insertion of Al3+ due to excessively strong adsorption, while allowing H3O+ to be inserted/diffused through the Grotthuss proton conduction mechanism. This research advances our understanding of the mechanism behind selective H3O+ insertion in mild electrolytes. [ABSTRACT FROM AUTHOR]

Atomically precise metal nanoclusters (NCs) with unique optical properties and abundant catalytic sites are promising in photocatalysis. However, their light‐induced instability and the difficulty of utilizing the photogenerated carriers for photocatalysis pose significant challenges. Here, MAg24 (M=Ag, Pd, Pt, and Au) NCs doped with diverse single heteroatoms have been encapsulated in a metal–organic framework (MOF), UiO‐66‐NH2, affording MAg24@UiO‐66‐NH2. Strikingly, compared with Ag25@UiO‐66‐NH2, the MAg24@UiO‐66‐NH2 doped with heteroatom exhibits much enhanced activity in photocatalytic hydrogen production, among which AuAg24@UiO‐66‐NH2 presents the best activity up to 3.6 mmol g−1 h−1, far superior to all other counterparts. Moreover, they display excellent photocatalytic recyclability and stability. X‐ray photoelectron spectroscopy and ultrafast transient absorption spectroscopy demonstrate that MAg24 NCs encapsulated into the MOF create a favorable charge transfer pathway, similar to a Z‐scheme heterojunction, when exposed to visible light. This promotes charge separation, along with optimized Ag electronic state, which are responsible for the superior activity in photocatalytic hydrogen production. [ABSTRACT FROM AUTHOR]

Circularly polarized luminescence (CPL) plays a pivotal role in cutting‐edge display and information technologies. Currently achieving precise color control and dynamic signal regulation in CPL still remains challenging due to the elusory relationship between fluorescence and chirality. Inspired by the natural mechanisms governing color formation and chiral interaction, we proposed an addition‐subtraction principle theory to address this issue. Three fluorene‐based polymers synthesized by Suzuki polycondensation with different electron‐deficient monomers exhibit similar structures and UV/Vis absorption, but distinct fluorescence emissions due to intramolecular charge transfer. Based on this, precise‐color CPL‐active films are obtained through quantitative supramolecular co‐assembly directed by addition principle. Particularly, an ideal white‐emitting CPL film (CIE coordinates: (0.33, 0.33)) is facilely fabricated with a high quantum yield of 80.8 % and a dissymmetry factor (glum) of 1.4×10−2. Structural analysis reveals that the ordered stacking orientation favors higher glum. Furthermore, to address the dynamically regulated challenge, the comparable subtraction principle is proposed, involving a contactless chiral communication between excited and ground states. The representative system consisting of as‐prepared fluorene‐based polymers and chirality‐selective absorption azobenzene (Azo)‐containing polymers is constructed, achieving CPL weakening, reversal, and enhancement. Finally, a switchable quick response code is realized based on trans‐cis isomerization of Azo moiety. [ABSTRACT FROM AUTHOR]

Due to multidrug resistance and the high risk of recurrence, effective and less toxic alternative pancreatic cancer treatments are urgently needed. Pancreatic cancer cells are highly resistant to apoptosis but sensitive to ferroptosis. In this study, an innovative nanoplatform (AsIr@PDA) was developed by electrostatic adsorption of a cationic iridium complex (IrFN) onto two‐dimensional (2D) arsenene nanosheets. This nanoplatform exhibits superior ferroptosis‐inducing effects with high drug loading capacity and, importantly, excellent anti‐cancer immune activation function, leading to efficient elimination of pancreatic tumors with no observable side effects. Interestingly, AsIr@PDA significantly prevents the recurrence of pancreatic cancer in vivo when compared with a cisplatin‐loaded nanoplatform. This designed nanoplatform demonstrated superior therapeutic efficacy by synergistic ferroptosis‐induced chemotherapy with immunotherapy via an all‐in‐one strategy, providing new insights for future pancreatic cancer therapy. [ABSTRACT FROM AUTHOR]

In contrast with the well‐established C(sp2)−SCF3 cross‐coupling to forge the Ar−SCF3 bond, the corresponding enantioselective coupling of readily available alkyl electrophiles to forge chiral C(sp3)−SCF3 bond has remained largely unexplored. We herein disclose a copper‐catalyzed enantioselective radical C(sp3)−SCF3 coupling of a range of secondary/tertiary benzyl radicals with the easily available (Me4N)SCF3 reagent. The key to the success lies in the utilization of chiral phosphino‐oxazoline‐derived anionic N,N,P‐ligands through tuning electronic and steric effects for the simultaneous control of the reaction initiation and enantioselectivity. This strategy can successfully realize two types of asymmetric radical reactions, including enantioconvergent C(sp3)−SCF3 cross‐coupling of racemic benzyl halides and three‐component 1,2‐carbotrifluoromethylthiolation of arylated alkenes under mild reaction conditions. It therefore provides a highly flexible platform for the rapid assembly of an array of enantioenriched SCF3‐containing molecules of interest in organic synthesis and medicinal chemistry. [ABSTRACT FROM AUTHOR]

In contrast with the well‐established C(sp2)−SCF3 cross‐coupling to forge the Ar−SCF3 bond, the corresponding enantioselective coupling of readily available alkyl electrophiles to forge chiral C(sp3)−SCF3 bond has remained largely unexplored. We herein disclose a copper‐catalyzed enantioselective radical C(sp3)−SCF3 coupling of a range of secondary/tertiary benzyl radicals with the easily available (Me4N)SCF3 reagent. The key to the success lies in the utilization of chiral phosphino‐oxazoline‐derived anionic N,N,P‐ligands through tuning electronic and steric effects for the simultaneous control of the reaction initiation and enantioselectivity. This strategy can successfully realize two types of asymmetric radical reactions, including enantioconvergent C(sp3)−SCF3 cross‐coupling of racemic benzyl halides and three‐component 1,2‐carbotrifluoromethylthiolation of arylated alkenes under mild reaction conditions. It therefore provides a highly flexible platform for the rapid assembly of an array of enantioenriched SCF3‐containing molecules of interest in organic synthesis and medicinal chemistry. [ABSTRACT FROM AUTHOR]

Oxygen reduction reaction (ORR) is of critical significance in the advancement of fuel cells and zinc‐air batteries. The iron‐nitrogen (Fe−Nx) sites exhibited exceptional reactivity towards ORR. However, the task of designing and controlling the local structure of Fe species for high ORR activity and stability remains a challenge. Herein, we have achieved successful immobilization of Fe species onto the highly curved surface of S, N co‐doped carbonaceous nanosprings (denoted as FeNS/Fe3C@CNS). The induction of this twisted configuration within FeNS/Fe3C@CNS arose from the assembly of chiral templates. For electrocatalytic ORR tests, FeNS/Fe3C@CNS exhibits a half‐wave potential (E1/2) of 0.91 V in alkaline medium and a E1/2 of 0.78 V in acidic medium. The Fe single atoms and Fe3C nanoparticles are coexistent and play as active centers within FeNS/Fe3C@CNS. The highly curved surface, coupled with S substitution in the coordination layer, served to reduce the energy barrier for ORR, thereby enhancing the intrinsic catalytic activity of the Fe single‐atom sites. We also assembled a wearable flexible Zn‐air battery using FeNS/Fe3C@CNS as electrocatalysts. This work provides new insights into the construction of highly curved surfaces within carbon materials, offering high electrocatalytic efficacy and remarkable performance for flexible energy conversion devices. [ABSTRACT FROM AUTHOR]

Addressing the limitations arising from the consistent catalytic behavior observed for various intermediates during the electrochemical carbon dioxide reduction reaction (CO2RR) poses a significant challenge in the optimization of catalytic activity. In this study, we aimed to address this challenge by constructing an asymmetric coordination Fe single atom catalyst (SCA) with a dynamically evolved structure. Our catalyst, consisting of a Fe atom coordinated with one S atom and three N atoms (Fe−S1N3), exhibited exceptional selectivity (CO Faradaic efficiency of 99.02 %) and demonstrated a high intrinsic activity (TOF of 7804.34 h−1), and remarkable stability. Using operando XAFS spectra and Density Functional Theory (DFT) calculations, we elucidated the self‐relaxation of geometric distortion and dynamic evolution of bond lengths within the catalyst. These structure changes enabled independent regulation of the *COOH and *CO intermediate adsorption energies, effectively breaking the linear scale relationship and enhancing the intrinsic activity of CO2RR. This study provides valuable insights into the dynamic evolution of SACs and paves the way for targeted catalyst designs aimed to disrupt the linear scaling relationships. [ABSTRACT FROM AUTHOR]

Unraveling the chirality transfer mechanism of polymer assemblies and controlling their handedness is beneficial for exploring the origin of hierarchical chirality and developing smart materials with desired chiroptical activities. However, polydisperse polymers often lead to an ambiguous or statistical evaluation of the structure–property relationship, and it remains unclear how the iterative number of repeating units function in the helicity inversion of polymer assemblies. Herein, we report the macroscopic helicity and dynamic manipulation of the chiroptical activity of supramolecular assemblies from discrete azobenzene‐containing oligomers (azooligomers), together with the helicity inversion and morphological transition achieved solely by changing the iterative chain lengths. The corresponding assemblies also differ from their polydisperse counterparts in terms of thermodynamic properties, chiroptical activities, and morphological control. [ABSTRACT FROM AUTHOR]

Atherosclerosis is a lipoprotein‐driven disease, and there is no effective therapy to reverse atherosclerosis or existing plaques. Therefore, it is urgently necessary to create a noninvasive and reliable approach for early atherosclerosis detection to prevent initial plaque formation. Atherosclerosis is intimately associated with inflammation, which is accompanied by an excess of reactive oxygen species (ROS), leading to cells requiring more glutathione (GSH) to resist severe oxidative stress. Therefore, the GSH‐hydrolyzed protein γ‐glutamyl transpeptidase (GGT) and the ROS‐hypobromous acid (HBrO) are potential biomarkers for predicting atherogenesis. Hence, to avoid false‐positive diagnoses caused by a single biomarker, we constructed an ingenious sequence‐activated double‐locked TP fluorescent probe, C‐HBrO‐GGT, in which two sequential triggers of GGT and HBrO are meticulously designed to ensure that the probe fluoresces in response to HBrO only after GGT hydrolyzes the probe. By utilization of C‐HBrO‐GGT, the voltage‐gated chloride channel (CLC‐1)‐HBrO‐catalase (CAT)‐GGT signaling pathway was confirmed in cellular level. Notably, the forthcoming atherosclerotic plaques were successfully predicted before the plaques could be observed via the naked eye or classical immunofluorescent staining. Collectively, this research proposed a powerful tool to indicate the precise position of mature plaques and provide early warning of atherosclerotic plaques. [ABSTRACT FROM AUTHOR]

Precise control over the chirality and morphologies of polymer assemblies, a remaining challenge for both chemists and materials scientists, is receiving ever‐increasing attention in the recent years. Herein, we report the subtle manipulation of the achiral spacers from the chiral stereocenter to the azobenzene (Azo) unit, of which the chiroptical consistency or chiroptical inversion of self‐assemblies could be successfully controlled and present "two‐fold" odd‐even effect. Furthermore, morphological transitions from 0D spherical micelles, 1D worms, and nanowires to 3D vesicles, spindle‐ and dumbbell‐shaped vesicles were also unexpectedly found to exhibit odd‐even correlations. These observations were collectively elucidated by mesomorphic properties, stacking modes, chiroptical dynamics, and stimuli‐responsive behaviors. Negligible modifications to the spacer structures can enable remarkable modulation of supramolecular chirality and anisotropic topologies in polymer assemblies, which is of great significance for the design of complex chiral functional polymers. [ABSTRACT FROM AUTHOR]