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A key challenge in efficient molecular separation is fabricating large‐scale, highly selective polymeric membranes with precise pore control at the molecular scale. Herein, a new contorted monomer 6,6′‐dihydroxy‐2,2′‐biphenyldiamine (DHBIPDA) is introduced as a building block to generate cross‐linked, ultra‐thin microporous nanofilms (sub‐10 nm) via interfacial polymerization, enabling rapid, and precise molecular nanofiltration. Using diacyl chloride (TPC) as the cross‐linker instead of trimesoyl chloride (TMC) significantly reduces the pore sizes within the membranes and achieves a narrower pore distribution due to a semi‐crystalline structure. The film structures are confirmed using comprehensive characterization techniques including wide‐angle X‐ray scattering (WAXS), X‐ray diffraction (XRD), positron annihilation lifetime spectroscopy (PALS), CO2 adsorption analysis, and molecular‐scale simulation. The DHBIPDA/TPC and DHBIPDA/TMC membranes achieve methanol permeance values of up to 16.4 and 15.1 LMH bar−1 coupled with molecular weight cutoffs (MWCOs) as low as 283 and 306 Da, respectively. The DHBIPDA/TPC membrane demonstrates both higher permeance and higher selectivity compared to its relatively disordered counterpart DHBIPDA/TMC, consistent with characterization data. The DHBIPDA‐derived membrane efficiently separates dye mixtures with similar molecular weights and enables effective recycling of organometallic homogeneous catalysts, suggesting its potential for industrial applications. [ABSTRACT FROM AUTHOR]

Cluster aggregation states are thermodynamically favored at the subnanoscale, for which an inverse growth from nanoparticles to clusters may be realized on subnanometer supports. Herein, we develop Au‐polyoxometalate‐layered double hydroxide (Au‐POM‐LDH) sub‐1 nm nanosheets (Sub‐APL) based on the above strategy, where sub‐1 nm Au clusters with negative valence are generated by the in situ disintegration of Au nanoparticles on POM‐LDH supports. Sub‐1 nm Au clusters with ultrahigh surface atom ratios exhibit remarkable efficiency for glutathione (GSH) depletion. The closely connected sub‐1 nm Au with negative valence and POM hetero‐units can promote the separation of hole‐electrons, resulting in the enhanced reactive oxygen species (ROS) generation under ultrasound (US). Besides, the reversible redox of Mo in POM is able to deplete GSH and trigger chemodynamic therapy (CDT) simultaneously, further enhancing the oxidative stress. Consequently, the Sub‐APL present 2‐fold ROS generation under US and 7‐fold GSH depletion compared to the discrete Au and POM‐LDH mixture. Therefore, the serious imbalance of redox in the TME caused by the sharp increase of ROS and rapid decrease of GSH leads to death of tumor ultimately. [ABSTRACT FROM AUTHOR]

It is a great challenge to integrate incompatible subunits into ordered macroscopic materials with tailored functionalities. Herein, a facile modular assembly strategy is demonstrated to link incompatible colloidal nanocrystals and polymer micelles by using the phenolic resol as the "molecule glue" for the synthesis of nanocrystal‐inserted mesoporous frameworks with diverse functionalities. It is found that the uniform nanocrystals can be inserted into the mesoporous frameworks with outstanding spatial dispersity, even in the case of high incorporation density. This modular assembly route is versatile, a library of nanocrystals with diverse diameters, shapes, and compositions can be integrated into various kinds of mesoporous frameworks (carbon, carbon‐SiO2, and carbon‐TiO2 composites). Unprecedently, this strategy also allows the controllable assembly of two, even three types of nanocrystals within the mesoporous frameworks to achieve multiple functionalities. The as‐prepared nanocomposites can simultaneously exhibit catalytic, magnetic, and adsorption properties independently, and show synergistic effects for tandem catalytic applications. [ABSTRACT FROM AUTHOR]

Aromatic amines are important commercial chemicals, but their carcinogenicity poses a threat to humans and other organisms, making their rapid quantitative detection increasingly urgent. Here, amorphous MoO3 (a‐MoO3) monolayers with localized surface plasmon resonance (LSPR) effect in the visible region are designed for the trace detection of carcinogenic aromatic amine molecules. The hot‐electron fast decay component of a‐MoO3 decreases from 301 fs to 150 fs after absorption with methyl orange (MO) molecules, indicating the plasmon‐induced hot‐electron transfer (PIHET) process from a‐MoO3 to MO. Therefore, a‐MoO3 monolayers present high SERS performance due to the synergistic effect of electromagnetic enhancement (EM) and PIHET, proposing the EM‐PIHET synergistic mechanism in a‐MoO3. In addition, a‐MoO3 possesses higher electron delocalization and electronic state density than crystal MoO3 (c‐MoO3), which is conducive to the PIHET. The limit of detection (LOD) for o‐aminoazotoluene (o‐AAT) is 10−9 M with good uniformity, acid resistance, and thermal stability. In this work, trace detection and identification of various carcinogenic aromatic amines based on a‐MoO3 monolayers is realized, which is of great significance for reducing cancer infection rates. [ABSTRACT FROM AUTHOR]

Solar‐driven CO2 reduction and water oxidation to liquid fuels represents a promising solution to alleviate energy crisis and climate issue, but it remains a great challenge for generating CH3OH and CH3CH2OH dominated by multi‐electron transfer. Single‐cluster catalysts with super electron acceptance, accurate molecular structure, customizable electronic structure and multiple adsorption sites, have led to greater potential in catalyzing various challenging reactions. However, accurately controlling the number and arrangement of clusters on functional supports still faces great challenge. Herein, we develop a facile electrosynthesis method to uniformly disperse Wells‐Dawson‐ and Keggin‐type polyoxometalates on TiO2 nanotube arrays, resulting in a series of single‐cluster functionalized catalysts P2M18O62@TiO2 and PM12O40@TiO2 (M=Mo or W). The single polyoxometalate cluster can be distinctly identified and serves as electronic sponge to accept electrons from excited TiO2 for enhancing surface‐hole concentration and promote water oxidation. Among these samples, P2Mo18O62@TiO2‐1 exhibits the highest electron consumption rate of 1260 μmol g−1 for CO2‐to‐CH3OH conversion with H2O as the electron source, which is 11 times higher than that of isolated TiO2 nanotube arrays. This work supplied a simple synthesis method to realize the single‐dispersion of molecular cluster to enrich surface‐reaching holes on TiO2, thereby facilitating water oxidation and CO2 reduction. [ABSTRACT FROM AUTHOR]

Exploiting emissive hydrophobic nanoclusters for hydrophilic applications remains a challenge because of photoluminescence (PL) quenching during phase transfer. In addition, the mechanism underlying PL quenching remains unclear. In this study, the PL‐quenching mechanism was examined by analyzing the atomically precise structures and optical properties of a surface‐engineered Ag29 nanocluster with an all‐around‐carboxyl‐functionalized surface. Specifically, phase‐transfer‐triggered PL quenching was justified as molecular decoupling, which directed an unfixed cluster surface and weakened the radiative transition. Furthermore, emission recovery of the quenched nanoclusters was accomplished by using a supramolecular recoupling approach through the glutathione‐addition‐induced aggregation of cluster molecules, wherein the restriction of intracluster motion and intercluster rotation strengthened the radiative transition of the clusters. The results of this work offer a new perspective on structure‐emission correlations for atomically precise nanoclusters and hopefully provide insight into the fabrication of highly emissive cluster‐based nanomaterials for downstream hydrophilic applications. [ABSTRACT FROM AUTHOR]

Self‐assembly of subnanometer (sub‐1 nm) scale polyhedral building blocks can yield some superstructures with novel and interesting morphology as well as potential functionalities. However, achieving the self‐assembly of sub‐1 nm polyhedral building blocks is still a great challenge. Herein, through encapsulating the titanium‐substituted polyoxometalate (POM, K7PTi2W10O40) with tetrabutylammonium cations (TBA+), we first synthesized a sub‐1 nm rhombic dodecahedral building block by further tailoring the spatial distribution of TBA+ on the POM. Molecular dynamics (MD) simulations demonstrated the eight TBA+ cations interacted with the POM cluster and formed the sub‐1 nm rhombic dodecahedron. As a result of anisotropy, the sub‐1 nm building blocks have self‐assembled into rhombic dodecahedral POM (RD‐POM) assemblies at the microscale. Benefiting from the regular structure, Br− ions, and abundant active sites, the obtained RD‐POM assemblies exhibit excellent catalytic performance in the cycloaddition of CO2 with epoxides without co‐catalysts. This work provides a promising approach to tailor the symmetry and structure of sub‐1 nm building blocks by tuning the spatial distribution of ligands, which may shed light on the fabrication of superstructures with novel properties by self‐assembly. [ABSTRACT FROM AUTHOR]

Here, we report the synthesis of chiral selenium nanoparticles (NPs) using cysteine and the interfacial assembly strategy to generate a self‐assembled nanomembrane on a large‐scale with controllable morphology and handedness. The selenide (Se) NPs exhibited circular dichroism (CD) bands in the ultraviolet and visible region with a maximum intensity of 39.96 mdeg at 388 nm and optical anisotropy factors (g‐factors) of up to 0.0013 while a self‐assembled monolayer nanomembrane exhibited symmetrical CD approaching 72.8 mdeg at 391 nm and g‐factors up to 0.0034. Analysis showed that a photocurrent of 20.97±1.55 nA was generated by the D‐nanomembrane when irradiated under light while the L‐nanomembrane generated a photocurrent of 20.58±1.36 nA. Owing to the asymmetric intensity of the photocurrent with respect to the handedness of the nanomembrane, an ultrasensitive recognition of enantioselective kynurenine (Kyn) was achieved by the ten‐layer (10L) D‐nanomembrane exhibiting a photocurrent for L‐kynurenine (L‐Kyn) that was 8.64‐fold lower than that of D‐Kyn, with a limit of detection (LOD) of 0.0074 nM for the L‐Kyn, which was attributed to stronger affinity between L‐Kyn and D‐Se NPs. Noticeably, the chiral Se nanomembrane precisely distinguished L‐Kyn in serum and cerebrospinal fluid samples from Alzheimer's disease patients and healthy subjects. [ABSTRACT FROM AUTHOR]

Transition metal oxide (TMO) anode materials in lithium‐ion batteries (LIBs) usually suffer from serious volume expansion leading to the pulverization of structures, further giving rise to lower specific capacity and worse cycling stability. Herein, by introducing polyoxometalate (POM) clusters into TMOs and precisely controlling the amount of POMs, the MnZnCuOx‐phosphomolybdic acid hybrid sub‐1 nm nanosheets (MZC‐PMA HSNSs) anode is successfully fabricated, where the special electron rich structure of POMs is conducive to accelerating the migration of lithium ions on the anode to obtain higher specific capacity, and the non‐covalent interactions between POMs and TMOs make the HSNSs possess excellent structural and chemical stability, thus exhibiting outstanding electrochemical performance in LIBs, achieving a high reversible capacity (1157 mAh g−1 at 100 mA g−1) and an admirable long‐term cycling stability at low and high current densities. [ABSTRACT FROM AUTHOR]

Flexible gas sensors play an indispensable role in diverse applications spanning from environmental monitoring to portable medical electronics. Full wearable gas monitoring system requires the collaborative support of high‐performance sensors and miniaturized circuit module, whereas the realization of low power consumption and sustainable measurement is challenging. Here, a self‐powered and reusable all‐in‐one NO2 sensor is proposed by structurally and functionally coupling the sensor to the battery, with ultrahigh sensitivity (1.92%/ppb), linearity (R2 = 0.999), ultralow theoretical detection limit (0.1 ppb), and humidity immunity. This can be attributed to the regulation of the gas reaction route at the molecular level. The addition of amphiphilic zinc trifluoromethanesulfonate (Zn(OTf)2) enables the H2O‐poor inner Helmholtz layer to be constructed at the electrode–gel interface, thereby facilitating the direct charge transfer process of NO2 here. The device is then combined with a well‐designed miniaturized low‐power circuit module with signal conditioning, processing and wireless transmission functions, which can be used as wearable electronics to realize early and remote warning of gas leakage. This study demonstrates a promising way to design a self‐powered, sustainable, and flexible gas sensor with high performance and its corresponding wireless sensing system, providing new insight into the all‐in‐one system of gas detection. [ABSTRACT FROM AUTHOR]

Stretchable, self‐healing, and breathable skin‐biomimetic‐sensing iontronics play an important role in human physiological signal monitoring and human–computer interaction. However, previous studies have focused on the mimicking of skin tactile sensing (pressure, strain, and temperature), and the development of more functionalities is necessary. To this end, a superior humidity‐sensitive ionic skin is developed based on a self‐healing, stretchable, breathable, and biocompatible polyvinyl alcohol–cellulose nanofibers organohydrogel film, showing a pronounced thickness‐dependent humidity‐sensing performance. The as‐prepared 62.47‐μm‐thick organohydrogel film exhibits a high response (25,000%) to 98% RH, excellent repeatability, and long‐term stability (120 days). Moreover, this ionic skin has excellent resistance to large mechanical deformation and damage, and the worn‐out material can still retain its humidity‐sensing capabilities after self‐repair. Humidity‐sensing mechanism studies show that the induced response is mainly related to the increase of proton mobility and interfacial charge transport efficiency after water adsorption. The superior humidity responsiveness is attributed to the reduced thickness and the increased specific surface area of the organohydrogel film, allowing real‐time recording of physiological signals. Notably, by combining with a self‐designed printed circuit board, a continuous and wireless respiration monitoring system is developed, presenting its great potential in wearable and biomedical electronics. [ABSTRACT FROM AUTHOR]

Polymer dielectrics with high breakdown strength (Eb) and high efficiency are urgently demanded in advanced electrical and electronic systems, yet their energy density (Ue) is limited due to low dielectric constant and high loss at elevated temperatures. Conventional inorganic fillers with diameters from nano to micrometers can only increase er at the cost of compromised Eb and Ue due to their poor compatibility with polymer matrix. Herein, hydroxyapa-tite (HAP) sub-nanowires with a diameter of "0.9 nm are incorporated in polyetherimide (PEI) matrix to form HAP/PEI sub-nanocomposites. er and Eb of the composites are concomitantly enhanced with only 0.5 wt.% of HAP sub-nanowires, leading to high Ue of 5.14 (@150 °C) and 3.1 J cm-3 (@200 °C] with efficiency of 90% and high-temperature stability up to 3 x 105 chargedischarge cycles at 200 °C. Microstructural analysis and molecular dynamics simulations indicate that the sub-nanowires with comparable diameter as polymer chains induce enormous interfacial area, substantially increase mobility of polymer chains and form dense traps for charge carriers. This work extends the current research scope of polymer-inorganics composite dielectrics to the sub-nano-level incorporation and provides a novel strategy for fabricating high performance polymer dielectrics at elevated temperatures [ABSTRACT FROM AUTHOR]

Sub‐nanowires (SNWs) exhibit great potential applications in nanocomposites owing to their high specific surface area, high flexibility, and similarity to polymer chains in dimension, which are a good entry point to bridge inorganic materials and polymer materials. Herein, we synthesized hydroxyapatite sub‐nanowires (HAP SNWs) and engineered hydroxyapatite sub‐nanowires/polyimide (HSP) gels and films by simple mixing of HAP SNWs and polyimide (PI). Benefiting from the interactions between HAP SNWs and PI, these nanocomposites were a continuous hybrid network. As the increase of HAP SNWs contents, the viscosity and modulus of HSP gels were greatly improved by one or two orders of magnitude compared with PI gel. HSP films not only maintained high transparency but also gained high haze, as well as exhibited enhanced Young's modulus. Thus, both HSP gels and films developed in this work are promising for various applications in coatings and high‐performance films. [ABSTRACT FROM AUTHOR]

Sub‐1 nm nanowires (SNWs) combine the properties of inorganic materials and polymers. They can be highly oriented through assembly, and can also be easily processed. Meanwhile, aggregation‐induced emission luminogens (AIEgens) show high potential for optical applications, but they are usually hard to process. The combination of SNWs and AIEgens can enrich both of their applications. In this study, we report that the fluorescence emission intensity of the AIEgens–SNW dispersion is dramatically enhanced due to the flexibility of SNWs. Furthermore, we fabricate two kinds of functional films with circularly polarized luminescence (CPL) and linearly polarized luminescence (LPL) activities. The construction of CPL materials didn't require any chiral chemicals. The construction of LPL materials didn't require an additional stretching process. As a result, we endowed common achiral AIEgens with a high dissymmetry factor of 0.033 and a polarization ratio of 0.44, respectively. [ABSTRACT FROM AUTHOR]

Harvesting solar energy for saline and polluted water purification is a sustainable and affordable solution to alleviate the stress on water shortages. However, the water evaporation rate relies on high optical intensity and suffers from inadequate energy conversion. Herein, a novel hybrid donor–acceptor dendritic nanosheets (denoted as DNS) composed of phosphomolybdic acid (PMA) clusters and porphyrin ligands is reported. Experimental results and molecular dynamics simulations indicate that the PMA and porphyrin are oriented attachment and assembled into a stable nanostructure. Benefiting from the advantages of the unique structure and photosensitive components, the DNS exhibits high evaporation rate of 2.23 kg m‐2 h‐1 with 90.9% energy efficiency under 1 sun irradiation. It is noteworthy that the evaporation performance is upgraded by innovative technology, and even under 0.5 sun that is close to the natural sunlight intensity, the evaporation rate reaches up to 1.31 kg m‐2 h‐1, which exceeds that of the vast majority of the reported evaporators. Furthermore, this evaporator also displays excellent seawater desalination and wastewater decontamination based on photo‐thermal distillation, highlighting its potential application toward water purification. [ABSTRACT FROM AUTHOR]

Shape‐selective catalysis plays a key role in chemical synthesis. Porous nanomaterials with uniform pore structures are ideal supports for metal nanoparticles (MNPs) to generate efficient shape‐selective catalysis. However, many commercial irregular porous nanomaterials face the challenge to realize satisfactory shape selectivity due to the lack of molecular sieving structures. Herein, we report a concept of creating shape selectivity in MNPs/porous nanomaterials through intentionally poisoning certain MNPs using suitable modifiers. The remaining MNPs within the substrates can cooperate with the channels to generate selectivity. Such a strategy not only applies to regular porous nanomaterials (such as MOFs, zeolites) but also extended to irregular porous nanomaterials (such as active carbon, P25). Potentially, the matching among different MNPs, corresponding modifiers, and porous nanomaterials makes our strategy promising in selective catalytic systems. [ABSTRACT FROM AUTHOR]

In nanoparticle self‐assembly, the current lack of strategy to modulate orientational order creates challenges in isolating large‐area plastic crystals. Here, we achieve two orientationally distinct supercrystals using one nanoparticle shape, including plastic crystals and uniform metacrystals. Our approach integrates multi‐faceted Archimedean polyhedra with molecular‐level surface polymeric interactions to tune nanoparticle orientational order during self‐assembly. Experiments and simulations show that coiled surface polymer chains limit interparticle interactions, creating various geometrical configurations among Archimedean polyhedra to form plastic crystals. In contrast, brush‐like polymer chains enable molecular interdigitation between neighboring particles, favoring consistent particle configurations and result in uniform metacrystals. Our strategy enhances supercrystal diversity for polyhedra comprising multiple nondegenerate facets. [ABSTRACT FROM AUTHOR]

The rational design of previously unidentified materials that could realize excellent electrochemical‐controlled optical and charge storage properties simultaneously, are especially desirable and useful for fabricating smart multifunctional devices. Here, a facile synthesis of a 1D π–d conjugated coordination polymer (Ni‐BTA) is reported, consisting of metal (Ni)‐containing nodes and organic linkers (1,2,4,5‐benzenetetramine), which could be easily grown on various substrates via a scalable chemical bath deposition method. The resulting Ni‐BTA film exhibits superior performances for both electrochromic and energy storage functions, such as large optical modulation (61.3%), high coloration efficiency (223.6 cm2 C−1), and high gravimetric capacity (168.1 mAh g−1). In particular, the Ni‐BTA film can maintain its electrochemical recharge‐ability and electrochromic properties even after 10 000 electrochemical cycles demonstrating excellent durability. Moreover, a smart energy storage indicator is demonstrated in which the energy storage states can be visually recognized in real time. The excellent electrochromic and charge storage performances of Ni‐BTA films present a great promise for Ni‐BTA nanowires to be used as practical electrode materials in various applications such as electrochromic devices, energy storage cells, and multifunctional smart windows. [ABSTRACT FROM AUTHOR]

A single‐step solution‐based strategy is used to obtain 2D Janus‐like free‐standing ultrathin nanosheets build from two structurally unrelated species, that is, polyoxomolybdate (POM) and CoO. A controlled 2D‐to‐1D morphological transition was achieved by judiciously adjusting the solvent choice. These POM‐CoO heterostructures can behave as an ideal catalyst for the epoxidation of styrene. Benefiting from their amphiphilic nature, these 2D POM‐CoO nanosheets have also been used as surfactant to emulsify immiscible solvents. It is anticipated that structurally diverse polyoxometalates will offer promise as design elements for variety of structurally and compositionally tunable van der Waals integrated heteromaterials having a broad range applications. [ABSTRACT FROM AUTHOR]

Conventional absorbing, reflective and scattering polarizers are facing various issues, such as severe optical loss, necessary oblique incidence, humidity sensitivity or aging‐caused failure. Subnanowires (SNWs) with polymer‐analogue properties, intrinsic order, and multi‐level interactions attract widespread attention as superior candidates for building blocks of polarizers. Herein, freestanding and flexible liquid crystal (LC)‐SNW films are prepared through a facile directional coating method, not only exhibiting good stability for water and repeated temperature fluctuations, but also showing good polarization performance for visible and near‐infrared (NIR) light, with the polarization degree (P) values of 93%, 84%, and 63% at the wavelengths of 580, 780 and 960 nm. And the average haze achieves 85%. The LC‐SNW films have great potential in applications for polarizers, holographic projection imaging and flexible optical devices. [ABSTRACT FROM AUTHOR]

Inorganic single crystals with anisotropic structures usually suffer from high brittleness and stiffness. Flexible polymers are used to replace inorganic crystals, but the hot‐stretching‐induced orientation process is tedious, and oriented molecular chains tend to revert to random coils during aging. To overcome these obstacles and using the similarities between sub‐1 nm nanowires (NWs) and linear polymers, we successfully fabricated anisotropic, transparent, flexible, and stable (ATFS) NW films with great potential for optical applications through a wet‐spinning method. The NW films show birefringence, and their birefractive index is higher than that of many polymers. They also showed polarized absorption of UV light and anisotropic scattering of visible light. The integrated films composed of NWs and quantum dots showed good fluorescence polarization. The tedious synthesis of quantum rods and fabrication of oriented polymer films can thus be avoided. [ABSTRACT FROM AUTHOR]

Enhancement of the semiconductor-molecule interaction, in particular, promoting the interfacial charge transfer process (ICTP), is key to improving the sensitivity of semiconductor-based surface enhanced Raman scattering (SERS). Herein, by developing amorphous ZnO nanocages (a-ZnO NCs), we successfully obtained an ultrahigh enhancement factor of up to 6.62×105. This remarkable SERS sensitivity can be attributed to high-efficiency ICTP within a-ZnO NC molecule system, which is caused by metastable electronic states of a-ZnO NCs. First-principles density functional theory (DFT) simulations further confirmed a stronger ICTP in a-ZnO NCs than in their crystalline counterparts. The efficient ICTP can even generate π bonding in Zn−S bonds peculiar to the mercapto molecule adsorbed a-ZnO NCs, which has been verified through the X-ray absorption near-edge structure (XANES) characterization. To the best of our knowledge, this is the first time such remarkable SERS activity has been observed within amorphous semiconductor nanomaterials, which could open a new frontier for developing highly sensitive and stable SERS technology. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) have drawn increasing attentions as promising candidates for functional devices. Herein, we present MOF films in constructing memory devices with alcohol mediated resistance switching property, where the resistance state is controlled by applying alcohol vapors to achieve multilevel information storage. The ordered packing mode and the hydrogen bonding system of the guest molecules adsorbed in MOF crystals are shown to be the reason for the alcohol mediated electrical switching. This chemically mediated memory device can be a candidate in achieving environment-responsive devices and exhibits potential applications in wearable information storage systems. [ABSTRACT FROM AUTHOR]

Exploiting emissive hydrophobic nanoclusters for hydrophilic applications remains a challenge because of photoluminescence (PL) quenching during phase transfer. In addition, the mechanism underlying PL quenching remains unclear. In this study, the PL‐quenching mechanism was examined by analyzing the atomically precise structures and optical properties of a surface‐engineered Ag29 nanocluster with an all‐around‐carboxyl‐functionalized surface. Specifically, phase‐transfer‐triggered PL quenching was justified as molecular decoupling, which directed an unfixed cluster surface and weakened the radiative transition. Furthermore, emission recovery of the quenched nanoclusters was accomplished by using a supramolecular recoupling approach through the glutathione‐addition‐induced aggregation of cluster molecules, wherein the restriction of intracluster motion and intercluster rotation strengthened the radiative transition of the clusters. The results of this work offer a new perspective on structure‐emission correlations for atomically precise nanoclusters and hopefully provide insight into the fabrication of highly emissive cluster‐based nanomaterials for downstream hydrophilic applications. [ABSTRACT FROM AUTHOR]