Glass transition temperature as a unified parameter to design self-healable elastomers.

Self-healing ability of materials, particularly polymers, improves their functional stabilities and lifespan. To date, the designs for self-healable polymers have relied on specific intermolecular interactions or chemistries. We report a design methodology for self-healable polymers based on glass transition. Statistical copolymer series of two monomers with different glass transition temperatures (Tg) were synthesized, and their self-healing tendency depends on the Tg of the copolymers and the constituents. Self-healing occurs more efficiently when the difference in Tg between two monomer units is larger, within a narrow Tg range of the copolymers, irrespective of their functional groups. The self-healable copolymers are elastomeric and nonpolar. The strategy to graft glass transition onto self-healing would expand the scope of polymer design.

Unveiling the Power of Cloaking Metal-Organic Framework Platforms via Supramolecular Antibody Conjugation.

Targeted drug delivery systems based on metal-organic frameworks (MOFs) have progressed tremendously since inception and are now widely applicable in diverse scientific fields. However, translating MOF agents directly to targeted drug delivery systems remains a challenge due to the biomolecular corona phenomenon. Here, we observed that supramolecular conjugation of antibodies to the surface of MOF particles (MOF-808) via electrostatic interactions and coordination bonding can reduce protein adhesion in biological environments and show stealth shields. Once antibodies are stably conjugated to particles, they were neither easily exchanged with nor covered by biomolecule proteins, which is indicative of the stealth effect. Moreover, upon conjugation of the MOF particle with specific targeted antibodies, namely, anti-CD44, human epidermal growth factor receptor 2 (HER2), and epidermal growth factor receptor (EGFR), the resulting hybrid exhibits an augmented targeting efficacy toward cancer cells overexpressing these receptors, such as HeLa, SK-BR-3, and 4T1, as evidenced by flow cytometry. The therapeutic effectiveness of the antibody-conjugated MOF (anti-M808) was further evaluated through in vivo imaging and the assessment of tumor inhibition effects using IR-780-loaded EGFR-M808 in a 4T1 tumor xenograft model employing nude mice. This study therefore provides insight into the use of supramolecular antibody conjugation as a promising method for developing MOF-based drug delivery systems.

Metallosupramolecular Multiblock Copolymers of Lanthanide Complexes by Seeded Living Polymerization.

Supramolecular block copolymers, derived via seeded living polymerization, are increasingly recognized for their rich structural and functional diversity, marking them as cutting-edge materials. The use of metal complexes in supramolecular block copolymerization not only offers a broad range of block copolymers through the structural similarity in the coordination geometry of the central metal ion but also controls spectroscopic properties, such as emission wavelength, emission strength, and fluorescence lifetime. However, the exploration of metallosupramolecular multiblock copolymerization based on metal complexes remains quite limited. In this work, we present a pioneering synthesis of metallosupramolecular multiblock copolymers utilizing Eu3+ and Tb3+ complexes as building blocks. This is achieved through the strategic manipulation of nonequilibrium self-assemblies via a living supramolecular polymerization approach. Our comprehensive exploration of both thermodynamically and kinetically regulated metallosupramolecular polymerizations, centered around Eu3+ and Tb3+ complexes with bisterpyridine-modified ligands containing R-alanine units and a long alkyl group, has highlighted intriguing behaviors. The monomeric [R-L1Eu(NO3)3] complex generates a spherical structure as the kinetic product. In contrast, the monomeric [R-L1Eu2(NO3)6] complex generates fiber aggregates as a thermodynamic product through intermolecular interactions such as π-π stacking, hydrophobic interaction, and H-bonds. Utilizing the Eu3+ complex, we successfully conducted seed-induced living polymerization of the monomeric building unit under kinetically regulated conditions. This yielded a metallosupramolecular polymer of precisely controlled length with minimal polydispersity. Moreover, by copolymerizing the kinetically confined Tb3+ complex state ("A" species) with a seed derived from the Eu3+ complex ("B" species), we were able to fabricate metallosupramolecular tri- and pentablock copolymers with A-B-A, and B-A-B-A-B types, respectively, through a seed-end chain-growth mechanism.

Abnormally High Graphitic Crystallization of Cellulose Nanocrystals.

Cellulose nanocrystals (CNCs) are currently of great interest for many applications, such as energy storage and nanocomposites, because of their natural abundance. A number of carbonization studies have reported abnormal graphitization behavior of CNCs, although cellulose is generally known as a precursor for hard carbon (nongraphitizable carbon). Herein, we report a spray-freeze-drying (SFD) method for CNCs and a subsequent carbonization study to ascertain the difference in the structural development between the amorphous and crystalline phases. The morphological observation by high-resolution transmission electron microscopy of the carbonized SFD-CNC clearly shows that the amorphous and crystalline phases of CNC are attributed to the formation of hard and soft carbon, respectively. The results of a reactive molecular dynamics (RMD) study also show that the amorphous cellulose phase leads to the formation of fewer carbon ring structures, indicative of hard carbon. In contrast, the pristine crystalline cellulose phase has a higher density and thermal stability, resulting in limited molecular relaxation and the formation of a highly crystalline graphitic structure (soft carbon).

Electrolyte Design for High-Voltage Lithium-Metal Batteries with Synthetic Sulfonamide-Based Solvent and Electrochemically Active Additives.

Considering practical viability, Li-metal battery electrolytes should be formulated by tuning solvent composition similar to electrolyte systems for Li-ion batteries to enable the facile salt-dissociation, ion-conduction, and introduction of sacrificial additives for building stable electrode-electrolyte interfaces. Although 1,2-dimethoxyethane with a high-donor number enables the implementation of ionic compounds as effective interface modifiers, its ubiquitous usage is limited by its low-oxidation durability and high-volatility. Regulation of the solvation structure and construction of well-structured interfacial layers ensure the potential strength of electrolytes in both Li-metal and LiNi0.8Co0.1Mn0.1O2 (NCM811). This study reports the build-up of multilayer solid-electrolyte interphase by utilizing different electron-accepting tendencies of lithium difluoro(bisoxalato) phosphate (LiDFBP), lithium nitrate, and synthetic 1-((trifluoromethyl)sulfonyl)piperidine. Furthermore, a well-structured cathode-electrolyte interface from LiDFBP effectively addresses the issues with NCM811. The developed electrolyte based on a framework of highly- and weakly-solvating solvents with interface modifiers enables the operation of Li|NCM811 cells with a high areal capacity cathode (4.3 mAh cm-2) at 4.4 V versus Li/Li+.

Compositionally Sequenced Interfacial Layers for High-Energy Li-Metal Batteries.

Electrolyte additives with multiple functions enable the interfacial engineering of Li-metal batteries (LMBs). Owing to their unique reduction behavior, additives exhibit a high potential for electrode surface modification that increases the reversibility of Li-metal anodes by enabling the development of a hierarchical solid electrolyte interphase (SEI). This study confirms that an adequately designed SEI facilitates the homogeneous supply of Li+, nonlocalized Li deposition, and low electrolyte degradation in LMBs while enduring the volume fluctuation of Li-metal anodes on cycling. An in-depth analysis of interfacial engineering mechanisms reveals that multilayered SEI structures comprising mechanically robust LiF-rich species, electron-rich P-O species, and elastic polymeric species enabled the stable charge and discharge of LMBs. The polymeric outer SEI layer in the as-fabricated multilayered SEI could accommodate the volume fluctuation of Li-metal anodes, significantly enhancing the cycling stability Li||LiNi0.8Co0.1Mn0.1O2 full cells with an electrolyte amount of 3.6 g Ah-1 and an areal capacity of 3.2 mAh cm-2. Therefore, this study confirms the ability of interfacial layers formed by electrolyte additives and fluorinated solvents to advance the performance of LMBs and can open new frontiers in the fabrication of high-performance LMBs through electrolyte-formulation engineering.

Direct Electrochemical Functionalization of Graphene Grown on Cu Including the Reaction Rate Dependence on the Cu Facet Type.

We present an electrochemical method to functionalize single-crystal graphene grown on copper foils with a (111) surface orientation by chemical vapor deposition (CVD). Graphene on Cu(111) is functionalized with 4-iodoaniline by applying a constant negative potential, and the degree of functionalization depends on the applied potential and reaction time. Our approach stands out from previous methods due to its transfer-free method, which enables more precise and efficient functionalization of single-crystal graphene. We report the suggested effects of the Cu substrate facet by comparing the reactivity of graphene on Cu(111) and Cu(115). The electrochemical reaction rate changes dramatically at the potential threshold for each facet. Kelvin probe force microscopy was used to measure the work function, and the difference in onset potentials of the electrochemical reaction on these two different facets are explained in terms of the difference in work function values. Density functional theory and Monte Carlo calculations were used to calculate the work function of graphene and the thermodynamic stability of the aniline functionalized graphene on these two facets. This study provides a deeper understanding of the electrochemical behavior of graphene (including single-crystal graphene) on Cu(111) and Cu(115). It also serves as a basis for further study of a broad range of reagents and thus functional groups and of the role of metal substrate beneath graphene.

Regulating electrostatic phenomena by cationic polymer binder for scalable high-areal-capacity Li battery electrodes.

Despite the enormous interest in high-areal-capacity Li battery electrodes, their structural instability and nonuniform charge transfer have plagued practical application. Herein, we present a cationic semi-interpenetrating polymer network (c-IPN) binder strategy, with a focus on the regulation of electrostatic phenomena in electrodes. Compared to conventional neutral linear binders, the c-IPN suppresses solvent-drying-induced crack evolution of electrodes and improves the dispersion state of electrode components owing to its surface charge-driven electrostatic repulsion and mechanical toughness. The c-IPN immobilizes anions of liquid electrolytes inside the electrodes via electrostatic attraction, thereby facilitating Li+ conduction and forming stable cathode-electrolyte interphases. Consequently, the c-IPN enables high-areal-capacity (up to 20 mAh cm-2) cathodes with decent cyclability (capacity retention after 100 cycles = 82%) using commercial slurry-cast electrode fabrication, while fully utilizing the theoretical specific capacity of LiNi0.8Co0.1Mn0.1O2. Further, coupling of the c-IPN cathodes with Li-metal anodes yields double-stacked pouch-type cells with high energy content at 25 °C (376 Wh kgcell-1/1043 Wh Lcell-1, estimated including packaging substances), demonstrating practical viability of the c-IPN binder for scalable high-areal-capacity electrodes.

Concurrent oxygen reduction and water oxidation at high ionic strength for scalable electrosynthesis of hydrogen peroxide.

Electrosynthesis of hydrogen peroxide via selective two-electron transfer oxygen reduction or water oxidation reactions offers a cleaner, cost-effective alternative to anthraquinone processes. However, it remains a challenge to achieve high Faradaic efficiencies at elevated current densities. Herein, we report that oxygen-deficient Pr1.0Sr1.0Fe0.75Zn0.25O4-δ perovskite oxides rich of oxygen vacancies can favorably bind the reaction intermediates to facilitate selective and efficient two-electron transfer pathways. These oxides exhibited superior Faradic efficiencies (~99%) for oxygen reduction over a wide potential range (0.05 to 0.45 V versus reversible hydrogen electrode) and current densities surpassing 50 mA cm-2 under high ionic strengths. We further found that the oxides perform a high selectivity (~80%) for two-electron transfer water oxidation reaction at a low overpotential (0.39 V). Lastly, we devised a membrane-free electrolyser employing bifunctional electrocatalysts, achieving a record-high Faradaic efficiency of 163.0% at 2.10 V and 50 mA cm-2. This marks the first report of the concurrent oxygen reduction and water oxidation catalysed by efficient bifunctional oxides in a novel membrane-free electrolyser for scalable hydrogen peroxide electrosynthesis.

Elucidating Ion Transport Phenomena in Sulfide/Polymer Composite Electrolytes for Practical Solid-State Batteries.

Despite the enormous interest in inorganic/polymer composite solid-state electrolytes (CSEs) for solid-state batteries (SSBs), the underlying ion transport phenomena in CSEs have not yet been elucidated. Here, we address this issue by formulating a mechanistic understanding of bi-percolating ion channels formation and ion conduction across inorganic-polymer electrolyte interfaces in CSEs. A model CSE is composed of argyrodite-type Li6PS5Cl (LPSCl) and gel polymer electrolyte (GPE, including Li+-glyme complex as an ion-conducting medium). The percolation threshold of the LPSCl phase in the CSE strongly depends on the elasticity of the GPE phase. Additionally, manipulating the solvation/desolvation behavior of the Li+-glyme complex in the GPE facilitates ion conduction across the LPSCl-GPE interface. The resulting scalable CSE (area = 8 × 6 (cm × cm), thickness ~ 40 µm) can be assembled with a high-mass-loading LiNi0.7Co0.15Mn0.15O2 cathode (areal-mass-loading = 39 mg cm-2) and a graphite anode (negative (N)/positive (P) capacity ratio = 1.1) in order to fabricate an SSB full cell with bi-cell configuration. Under this constrained cell condition, the SSB full cell exhibits high volumetric energy density (480 Wh Lcell-1) and stable cyclability at 25 °C, far exceeding the values reported by previous CSE-based SSBs.

Intra-Lysosomal Peptide Assembly for the High Selectivity Index against Cancer.

Lysosomes remain powerful organelles and important targets for cancer therapy because cancer cell proliferation is greatly dependent on effective lysosomal function. Recent studies have shown that lysosomal membrane permeabilization induces cell death and is an effective way to treat cancer by bypassing the classical caspase-dependent apoptotic pathway. However, most lysosome-targeted anticancer drugs have very low selectivity for cancer cells. Here, we show intra-lysosomal self-assembly of a peptide amphiphile as a powerful technique to overcome this problem. We designed a peptide amphiphile that localizes in the cancer lysosome and undergoes cathepsin B enzyme-instructed supramolecular assembly. This localized assembly induces lysosomal swelling, membrane permeabilization, and damage to the lysosome, which eventually causes caspase-independent apoptotic death of cancer cells without conventional chemotherapeutic drugs. It has specific anticancer effects and is effective against drug-resistant cancers. Moreover, this peptide amphiphile exhibits high tumor targeting when attached to a tumor-targeting ligand and causes significant inhibition of tumor growth both in cancer and drug-resistant cancer xenograft models.

A Phosphorofluoridate-Based Multifunctional Electrolyte Additive Enables Long Cycling of High-Energy Lithium-Ion Batteries.

Ni-rich layered oxides are regarded as key components for realizing post Li-ion batteries (LIBs). However, high-valence Ni, which acts as an oxidant in deeply delithiated states, aggravates the oxidation of the electrolyte at the cathode, causing cell impedance to increase. Additionally, the leaching of transition metal (TM) ions from Ni-rich cathodes by acidic compounds such as Brønsted-acidic HF produced through LiPF6 hydrolysis aggravates the structural instability of the cathode and renders the electrode-electrolyte interface unstable. Herein, we present a multifunctional electrolyte additive, bis(trimethylsilyl) phosphorofluoridate (BTSPFA), to attain enhanced interfacial stability of graphite anodes and Ni-rich cathodes in Li-ion cells. BTSPFA eliminates the corrosive HF molecules by cleaving silyl ether bonds and enables the formation of a polar P-O- and P-F-enriched cathode electrolyte interface (CEI) on the Ni-rich cathode. It also promotes the creation of a solid electrolyte interphase composed of inorganic-rich species, which suppresses the reduction of the electrolyte during battery operation. The synergistic effect of the HF scavenging ability of BTSPFA and the stable BTSPFA-promoted CEI effectively suppresses the TM leaching from the Ni-rich cathode while also preventing unwanted TM deposition on the anode. LiNi0.8Co0.1Mn0.1O2/graphite full cells with 1 wt % BTSPFA exhibited an enhanced discharge capacity retention of 79.8% after 500 cycles at 1C and 45 °C. These unique features of BTSPFA are useful for resolving the interfacial deterioration issue of high-capacity Ni-rich cathodes paired with graphite anodes.

Direct measurements of the colloidal Debye force.

Colloids often behave in a manner similar to their counterparts in molecular space and are used as model systems to understand molecular behavior. Here, we study like-charged colloidal attractions between a permanent dipole on an interfacial particle and its induced dipole on a water-immersed particle caused by diffuse layer polarization. We find that the scaling behavior of the measured dipole-induced dipole (D‒I) interaction via optical laser tweezers is in good agreement with that predicted from the molecular Debye interaction. The dipole character propagates to form aggregate chains. Using coarse-grained molecular dynamic simulations, we identify the separate roles of the D‒I attraction and the van der Waals attraction on aggregate formation. The D‒I attraction should be universal in a broad range of soft matter, such as colloids, polymers, clays, and biological materials, motivating researchers to further conduct in-depth research on these materials.

Design of Pore Properties of an Al-Based Metal-Organic Framework for the Separation of an Ethane/Ethylene Gas Mixture via Ethane-Selective Adsorption.

A series of Al-based isomorphs (CAU-10H, MIL-160, KMF-1, and CAU-10pydc) were synthesized using isophthalic acid (ipa), 2,5-furandicarboxylic acid (fdc), 2,5-pyrrole dicarboxylic acid (pyrdc), and 3,5-pyridinedicarboxylic acid (pydc), respectively. These isomorphs were systematically investigated to identify the best adsorbent for effectively separating C2H6/C2H4. All CAU-10 isomorphs exhibited preferential adsorption of C2H6 over that of C2H4 in mixture. CAU-10pydc exhibited the best C2H6/C2H4 selectivity (1.68) and the highest C2H6 uptake (3.97 mmol g-1) at 298 K and 1 bar. In the breakthrough experiment using CAU-10pydc, 1/1 (v/v) and 1/15 (v/v) C2H6/C2H4 gas mixtures were successfully separated into high-purity C2H4 (>99.95%), with remarkable productivities of 14.0 LSTP kg-1 and 32.0 LSTP kg-1, respectively, at 298 K. Molecular simulations revealed that the exceptional separation performance of CAU-10pydc originated from the increased porosity and reduced electron density of the pyridine ring of pydc, leading to a relatively larger decrease in π-π interactions with C2H4 than in the C-H···π interactions with C2H6. This study demonstrates that the pore size and geometry of the CAU-10 platform are modulated by the inclusion of heteroatom-containing benzene dicarboxylate or heterocyclic rings of dicarboxylate-based organic linkers, thereby fine-tuning the C2H6/C2H4 separation ability. CAU-10pydc was determined to be an optimum adsorbent for this challenging separation.

Protein-Precoated Surface of Metal-Organic Framework Nanoparticles for Targeted Delivery.

Metal-organic framework (MOF) nanoparticles have recently emerged as a promising vehicle for drug delivery with high porosity and feasibility. However, employing a MOF-based drug delivery system remains a challenge due to the difficulty in controlling interfaces of particles in a biological environment. In this paper, protein corona-blocked Zr6 -based MOF (PCN-224) nanoparticles are presented for targeted cancer therapy with high efficiency. The unmodified PCN-224 surface is precoated with glutathione transferase (GST)-fused targetable affibody (GST-Afb) proteins via simple mixing conjugations instead of chemical modifications that can induce the impairment of proteins. GST-Afb proteins are shown to stably protect the surface of PCN-224 particles in a specific orientation with GST adsorbed onto the porous surface and the GST-linked Afb posed outward, minimizing the unwanted interfacial interactions of particles with external biological proteins. The Afb-directed cell-specific targeting ability of particles and consequent induction of cell death is demonstrated both in vitro and in vivo by using two kinds of Afb, which targets the surface membrane receptor, human epidermal growth factor receptor 2 (HER2) or epidermal growth factor receptor (EGFR). This study provides insight into the way of regulating the protein-adhesive surface of MOF nanoparticles and designing a more effective MOF-hosted targeted delivery system.

Remarkable Electrical Conductivity Increase and Pure Metallic Properties from Semiconducting Colloidal Nanocrystals by Cation Exchange for Solution-Processable Optoelectronic Applications.

The authors report a strategic approach to achieve metallic properties from semiconducting CuFeS colloidal nanocrystal (NC) solids through cation exchange method. An unprecedentedly high electrical conductivity is realized by the efficient generation of charge carriers onto a semiconducting CuS NC template via minimal Fe exchange. An electrical conductivity exceeding 10 500 S cm-1 (13 400 S cm-1 at 2 K) and a sheet resistance of 17 Ω/sq at room temperature, which are among the highest values for solution-processable semiconducting NCs, are achieved successfully from bornite-phase CuFeS NC films possessing 10% Fe atom. The temperature dependence of the corresponding films exhibits pure metallic characteristics. Highly conducting NCs are demonstrated for a thermoelectric layer exhibiting a high power factor over 1.2 mW m-1 K-2 at room temperature, electrical wires for switching on light emitting diods (LEDs), and source-drain electrodes for p- and n-type organic field-effect transistors. Ambient stability, eco-friendly composition, and solution-processability further validate their sustainable and practical applicability. The present study provides a simple but very effective method for significantly increasing charge carrier concentrations in semiconducting colloidal NCs to achieve metallic properties, which is applicable to various optoelectronic devices.

Self-Accommodation Induced Electronic Metal-Support Interaction on Ruthenium Site for Alkaline Hydrogen Evolution Reaction.

Tuning the metal-support interaction of supported metal catalysts has been found to be the most effective approach to modulating electronic structure and improving catalytic performance. But practical understanding of the charge transfer mechanism at the electronic level of catalysis process has remained elusive. Here, it is reported that ruthenium (Ru) nanoparticles can self-accommodate into Fe3 O4 and carbon support (Ru-Fe3 O4 /C) through the electronic metal-support interaction, resulting in robust catalytic activity toward the alkaline hydrogen evolution reaction (HER). Spectroscopic evidence and theoretical calculations demonstrate that electronic perturbation occurred in the Ru-Fe3 O4 /C, and that charge redistribution directly influenced adsorption behavior during the catalytic process. The RuO bond formed by orbital mixing changes the charge state of the surface Ru site, enabling more electrons to flow to H intermediates (H* ) for favorable adsorption. The weak binding strength of the RuO bond also reinforces the anti-bonding character of H* with a more favorable recombination of H* species into H2 molecules. Because of this satisfactory catalytic mechanism, the Ru-Fe3 O4 /C supported nanoparticle catalyst demonstrated better HER activity and robust stability than the benchmark commercial Pt/C benchmark in alkaline media.

Tuning functionalized hexagonal boron nitride quantum dots for full visible-light fluorescence emission.

Tunable photoluminescence has been observed in hexagonal boron nitride quantum dots (BNQDs), but the underlying luminescence mechanism remains elusive. In this study, we examine excited-state properties of several functionalized BNQDs models using density functional theory (DFT), time-dependent DFT, and multistate complete active space second-order perturbation theory (MS-CASPT2) methods. Unlike reported graphene quantum dots, photoluminescence of BNQDs is not affected by their sizes (<2.5 nm). Instead, the embedded single sp3 carbon atom connecting different functional groups can tune emission colors of BNQDs, whose emission wavelength cover full range of visible light and even extend toward near-infrared region. Further analysis reveals that both exciton self-trapping and electron-hole separation decrease HOMO-LUMO energy gaps, leading to large Stokes shifts. Moreover, uneven and even hybridizations induce blue- and red-shifted emission spectra. These findings provide novel insights into full-spectrum emission of BNQDs modified with functional groups.

Photosensitive ion channels in layered MXene membranes modified with plasmonic gold nanostars and cellulose nanofibers.

Ion channels transduce external stimuli into ion-transport-mediated signaling, which has received considerable attention in diverse fields such as sensors, energy harvesting devices, and desalination membrane. In this work, we present a photosensitive ion channel based on plasmonic gold nanostars (AuNSs) and cellulose nanofibers (CNFs) embedded in layered MXene nanosheets. The MXene/AuNS/CNF (MAC) membrane provides subnanometer-sized ionic pathways for light-sensitive cationic flow. When the MAC nanochannel is exposed to NIR light, a photothermal gradient is formed, which induces directional photothermo-osmotic flow of nanoconfined electrolyte against the thermal gradient and produces a net ionic current. MAC membrane exhibits enhanced photothermal current compared with pristine MXene, which is attributed to the combined photothermal effects of plasmonic AuNSs and MXene and the widened interspacing of the MAC composite via the hydrophilic nanofibrils. The MAC composite membranes are envisioned to be applied in flexible ionic channels with ionogels and light-controlled ionic circuits.

Synthesis of Thermally Stable and Highly Luminescent Cs5 Cu3 Cl6 I2 Nanocrystals with Nonlinear Optical Response.

Low-dimensional Cu(I)-based metal halide materials are gaining attention due to their low toxicity, high stability and unique luminescence mechanism, which is mediated by self-trapped excitons (STEs). Among them, Cs5 Cu3 Cl6 I2 , which emits blue light, is a promising candidate for applications as a next-generation blue-emitting material. In this article, an optimized colloidal process to synthesize uniform Cs5 Cu3 Cl6 I2 nanocrystals (NCs) with a superior quantum yield (QY) is proposed. In addition, precise control of the synthesis parameters, enabling anisotropic growth and emission wavelength shifting is demonstrated. The synthesized Cs5 Cu3 Cl6 I2 NCs have an excellent photoluminescence (PL) retention rate, even at high temperature, and exhibit high stability over multiple heating-cooling cycles under ambient conditions. Moreover, under 850-nm femtosecond laser irradiation, the NCs exhibit three-photon absorption (3PA)-induced PL, highlighting the possibility of utilizing their nonlinear optical properties. Such thermally stable and highly luminescent Cs5 Cu3 Cl6 I2 NCs with nonlinear optical properties overcome the limitations of conventional blue-emitting nanomaterials. These findings provide insights into the mechanism of the colloidal synthesis of Cs5 Cu3 Cl6 I2 NCs and a foundation for further research.