Reversible Coordination Research Articles

Navigating the Challenges and Seizing Opportunities in Implementing Closed-Loop Supply Chains

Closed-Loop Supply Chains (CLSCs) present a transformative solution for industries seeking sustainability by reintegrating returned products through recycling, refurbishment, and remanufacturing, reducing waste and dependency on added resources. While offering substantial benefits, CLSC adoption faces challenges, including high infrastructure costs, complex reverse coordination, and inconsistent regulatory support, which hinder widespread application. Through a mixed-method approach using surveys and case studies, this study reveals barriers such as financial constraints and operational restructuring needs, while highlighting enablers like digital tools (e.g., blockchain, IoT) that enhance efficiency and transparency. Furthermore, it emphasizes the critical role of regulatory incentives (subsidies, tax breaks, and extended producer responsibility mandates) and strategic partnerships that pool resources and share risks, essential for small and medium-sized enterprises (SMEs) aiming to implement CLSCs effectively. By proposing a practical CLSC framework, informed by empirical data, this research provides actionable insights for businesses to embrace circular economy principles, aligning environmental responsibility with corporate resilience, profitability, and consumer expectations. CLSCs, therefore, are not only an environmental solution but also a strategic opportunity that addresses sustainability imperatives while meeting regulatory requirements and advancing competitive advantage.

Stability Assessment in Aqueous and Organic Solvents of Metal-Organic Framework PCN 333 Nanoparticles through a Combination of Physicochemical Characterization and Computational Simulations.

Mesoporous metal-organic frameworks (MOFs) have been recognized as powerful platforms for drug delivery, especially for biomolecules. Unfortunately, the application of MOFs is restricted due to their relatively poor stability in aqueous media, which is crucial for drug delivery applications. An exception is the porous coordination network (PCN)-series (e.g., PCN-333 and PCN-332), a series of MOFs with outstanding stability in aqueous media at the pH range from 3 to 9. In this study, we fabricate PCN-333 nanoparticles (nPCN) and investigate their stability in different solvents, including water, ethanol, and methanol. Surprisingly, the experimental characterizations in terms of X-ray diffraction, Brunauer-Emmett-Teller (BET), and scanning electron microscopy demonstrated that nPCN is not as stable in water as previously reported. Specifically, the crystalline structure of nPCN lost its typical octahedral shape and even decomposed into an irregular amorphous form when exposed to water for only 2 h, but not when ethanol and methanol were used. Meanwhile, the porosity of nPCN substantially diminished while being exposed to water, as demonstrated by the BET measurement. With the assistance of computational simulations, the mechanism behind the collapse of PCN-333 is illuminated. By molecular dynamics simulation and umbrella sampling, we elucidate that the degradation of PCN-333 occurs by hydrolysis, wherein polar solvent molecules initiate the attack and subsequent breakage of the metal-ligand reversible coordination bonds.

3D-printed redox-active polymer electrode with high-mass loading for ultra-low temperature proton pseudocapacitor

The stable operation of supercapacitors at extremely low temperatures is crucial for applications in harsh environments. Unfortunately, conventional inorganic electrodes suffer from sluggish diffusion kinetics and poor cycling stability for proton pseudocapacitors. Here, a redox-active polymer poly(1,5-diaminonaphthalene) is developed and synthesized as an ultrafast, high-mass loading, and durable pseudocapacitive anode. The charge storage of poly(1,5-diaminonaphthalene) depends on the reversible coordination reaction of the C=N group with H+, which enables fast kinetics associated with surface-controlled reactions. The 3D-printed organic electrode delivers a remarkable areal capacitance (8.43 F cm–2 at 30.78 mg cm−2) and thickness-independent rate performance. Furthermore, the 3D-printed proton pseudocapacitor exhibits great low-temperature tolerance and delivers a high energy density of 0.44 mWh cm−2 at −60 °C, as well as operates well even at −80 °C. This work signifies that combining organic material design with 3D hierarchical network electrode construction can provide a promising solution for low-temperature-resistant supercapacitors.

A Self-Healing and Sweat-Chargeable Hydrogel Electrolyte for All-in-One Flexible Supercapacitors.

Flexible solid-state supercapacitors (SCs) with hydrogel as an electrolyte and separator combine the advantages of wearability and energy storage and exhibit a broad application prospect in wearable energy textiles. However, irreversible electrolyte damage and unstable electrode-electrolyte interfaces during mechanical deformations remain bottlenecks in realizing truly wearable applications. Herein, poly(acrylic acid) (PAA)-Fe hydrogels were prepared through a simple thermal polymerization strategy. The dynamic reversible metal coordination bonds between Fe3+ and carboxylic acids confers the hydrogels with excellent self-healing properties. As expected, the prepared hydrogels exhibited superior mechanical strength (tensile stress of 45.80 kPa), ionic conductivity (0.076 S cm-1), and self-healing properties. Subsequently, the SCs were constructed using composite hydrogel electrodes (MnO2@CC embedded in the PAA-Fe hydrogels) as symmetrical electrodes (marked as MSCs). The reversible metal coordination bonds between composite hydrogel electrodes formed an ultrastable electrode/electrolyte interface in the all-in-one MSCs, thus revealing excellent mechanical durability. The all-in-one MSCs delivered a remarkable specific capacitance (30.98 F g-1 at 0.2 A g-1), excellent cyclic stability (87.24% after 5000 cycles), outstanding mechanical deformation stability, and impressive electrochemical output stability after self-healing (capacitance retention of 85.34% after five cycles of cutting/self-healing). It is noteworthy that the all-in-one MSCs employed NaCl as an electrolyte, which can be obtained from human sweat. As a proof of the self-charged concept, the all-in-one MSCs can be reused in sweat, whose capacitance was maintained at 90.05% of the initial state after three repetitions. This work is expected to shine light into the design of all-in-one and fabric-based SCs and the development of wearable energy textiles.

Multifaceted regulation of chiroptical properties and self‐assembly behaviors of chiral fluorescent polymers

AbstractThe multifaceted regulation of the chiroptical properties and self‐assembly behaviors of chiral fluorescent polymers is of great significance yet remains challenging to achieve. Herein, a series of novel salen‐based chiral fluorescent polymers with aggregation‐induced emission and varied substitution manners were facilely and efficiently synthesized. Multiple factors were systematically investigated on the chiroptical properties and self‐assembly performance of these polymers, which include molecular structures, solvent environments, metal coordination, and liquid crystal (LC) assemblies. Sutle change in the solvent composition can lead to diverse assembly morphologies of all these chiral polymers, from single‐handed helical fibers, helical toroids or loops, to spherical structures, consequently leading to an aggregation‐reduced circular dichroism (CD) phenomenon. The polymers bearing salen units show highly selective and reversible coordination with Zn2+ and can also induce multiple responses in the absorption, luminescence, CD, and circularly polarized luminescence (CPL) of these chiral fluorescent polymers via a coordination‐ and dissociation‐initiated self‐assembly tuning. Furthermore, a small amount of the chiral fluorescent polymer in can induce achiral nematic 4‐cyano‐4′‐n‐pentylbiphenyl (5CB) to form ordered chiral nematic LC phase with significant improvement in their CD and CPL signal. The absolute absorption and luminescent dissymmetry factors of the resulting supramolecular assemblies can reach the order of 10−1.

Ordered Carbonaceous Framework Synthesized from Hexaazatrinaphthylene with Enediyne Groups via Solid-State Bergman Cyclization Reaction.

Porous materials synthesized through bottom-up approaches, such as metal-organic frameworks and covalent organic frameworks, have attracted attention owing to their design flexibility for functional materials. However, achieving the chemical and thermal stability of these materials for various applications is challenging considering the reversible coordination bonds and irreversible covalent bonds in their frameworks. Thus, ordered carbonaceous frameworks (OCFs) emerge as a promising class of bottom-up materials with good periodicity, thermal and chemical stability, and electrical conductivity. However, a few OCFs have been reported owing to the limited range of precursor molecules. Herein, we designed a hexaazatrinaphthylene-based molecule with enediyne groups as a precursor molecule for synthesizing an OCF. The solid-state Bergman cyclization of enediyne groups at a low temperature formed a microporous polymer and an OCF, exhibiting redox activity and demonstrating their potential for electrochemical applications. The microporous polymer was used as an active material in sodium-ion batteries, while the OCF was used as an electrochemical capacitor. These findings illustrate the utility of the Bergman cyclization reaction for synthesizing microporous polymers and OCFs with a customizable functionality for broad applications.

Biomimetic Exploration and Reflection on Switchable Coordination and Narrow-Band Electrofluorochromic Devices.

Electrofluorochromic (EFC) materials and devices with controllable fluorescence properties show great application potential in advanced anticounterfeiting, information storage and display. However, the low color purity caused by the broad emission spectra and underperforming switching time of the existing EFC materials limit their application. Through biomimetic exploration and the study of reversible electrochemical responsive coordination reactions, boron-nitrogen embedded polyaromatics (B,N-PAHs) with narrow-band emission and high color purity have been successfully integrated into EFC systems, which also help to better understand the role of boron in biological activity. The EFC device achieve good performance containing quenching efficiency greater than 90% within short switching time (ton: 0.6s, toff: 2.4s), and nearly no performance change after 200 cycles test. Three primary color (red, green, and blue) EFC devices are successfully prepared. In addition, new phenomena are obtained and discussed in this biomimetic exploration of related boron reactions. The success and harvest of this exploration are expected to provide new ideas for optimizing properties and broadening applications of EFC materials. Moreover, it may provide ideas and reference significance for further exploring and understanding the function of boron compounds in biological systems.

Nucleophilic Aromatic Substitution of Halobenzenes and Phenols with Catalysis by Arenophilic π Acids.

ConspectusLewis π acids, particularly high-valent transition metals with vacant orbitals, can coordinate with unsaturated compounds such as alkynes and alkenes by means of π-bonding. The coordination enhances the electrophilicity of the bound compounds, thereby facilitating reactions─such as nucleophilic addition─that take place at the ligated carbon-carbon multiple bonds. This activation phenomenon occurs at the ligand rather than at the metal atom, and it has been extensively utilized in the development of catalytic methods. In addition to alkynes and alkenes, aromatic compounds featuring a phenyl ring can be activated by an electrophilic transition-metal unit (e.g., Cr(CO)3, [Mn(CO)3]+, [CpFe]+, or [CpRu]+, where Cp = cyclopentadienyl) through π coordination. Over the past several decades, remarkable advances have been achieved in the development of reactions occurring on bound arenes, capitalizing on the highly electron-withdrawing nature of these transition-metal units and on the thermodynamic stability of η6-arene complexes. A prime example is the extension of nucleophilic aromatic substitution (SNAr) reactions to electron-neutral and -rich halobenzenes. Such arenes, which are normally inert to classical SNAr, can undergo sequences involving complex formation, substitution, and complex decomposition. Despite the successes achieved through the utilization of preformed complexes, the application of reversible arene coordination to catalytic systems has seen only limited progress. Consequently, in π-coordination activation, transition-metal units are commonly considered to be components of bound arene complexes rather than π-acid catalysts.In this Account, we summarize our recent research on catalytic SNAr reactions of halobenzenes and phenols enabled by reversible π-coordination of the arenes with electrophilic Ru or Rh catalysts, which we refer to as arenophilic π-acids. First, we developed a method for SNAr amination of fluorobenzenes with catalysis by a Ru(II) complex with a hemilabile P,O-bidentate ligand. The use of the hemilabile ligand significantly enhanced catalytic efficiency, allowing electron-rich and -neutral arenes to undergo amination without the need of excess fluorobenzenes. In a subsequent study of hydroxylation and alkoxylation reactions, we found that Rh(III) catalysts bearing a Cp-type ligand had a substantial activating effect. In addition, by isolating an η5 complex as the reaction intermediate, we obtained evidence in support of the long-standing hypothesis that SNAr of η6-arene complexes proceeds via a stepwise mechanism. Next, we extended the Rh-catalyzed SNAr to chloro- and bromobenzenes, which are abundant and readily available but are less reactive than corresponding fluorides toward SNAr. When the weakly nucleophilic alcohol hexafluoroisopropanol was used as a reaction partner, we were able to synthesize hexafluoroisopropyl aryl ethers, which are challenging to obtain by means of conventional approaches. Beyond halobenzenes, we successfully applied π-coordination strategy to achieve umpolung substitution reactions of phenols, which are typically nucleophilic. We found that an arenophilic Rh or Ru catalyst activated the phenol ring by π coordination instead of κ-O coordination, generating transient η5-phenoxo complexes that subsequently underwent carbonyl-amine condensation to produce anilines without the need for an exogenous oxidant or reductant. We anticipate that our research on catalyst development and reactions involving π-coordination activation will facilitate further advances in the application of arenophilic π acids.

Ultra-adherable dual-network conductive hydrogel with moistening and anti-freezing as a flexible sensor

Multifunctional conductive hydrogels have shown great promise in wearable flexible sensor application. This paper reported a dual-network self-healing electrically hydrogel through simple one-pot polymerization, which initiated from Ag+- lignin nanoparticles (LNPs) -APS redox system. Owing to the reversible metal coordination and hydrogen bonding cross-linked among polymer network, the resulting conductive hydrogel-based sensor demonstrated excellent stretchable, adhesion strength, and fatigue resistance. Additionally, the complex hydrogel (PHEMA/SA/Gly/Ca) incorporating with glycerol and CaCl2 in particular exhibited strong frost resistance (−40oC) and moisturizing qualities to monitor the motion signals in the low-temperature dry state. Therefore, the fabricated wearable sensor is sufficient for detecting large and small human motions, suggesting lots of promising applications in electronic skins, information identification and encryption, and human-motion monitoring.

Ag–thiolate interactions to enable an ultrasensitive and stretchable MXene strain sensor with high temporospatial resolution

High-sensitivity strain sensing elements with a wide strain range, fast response, high stability, and small sensing areas are desirable for constructing strain sensor arrays with high temporospatial resolution. However, current strain sensors rely on crack-based conductive materials having an inherent tradeoff between their sensing area and performance. Here, we present a molecular-level crack modulation strategy in which we use layer-by-layer assembly to introduce strong, dynamic, and reversible coordination bonds in an MXene and silver nanowire-matrixed conductive film. We use this approach to fabricate a crack-based stretchable strain sensor with a very small sensing area (0.25 mm2). It also exhibits an ultrawide working strain range (0.001–37%), high sensitivity (gauge factor ~500 at 0.001% and >150,000 at 35%), fast response time, low hysteresis, and excellent long-term stability. Based on this high-performance sensing element and facile assembly process, a stretchable strain sensor array with a device density of 100 sensors per cm2 is realized. We demonstrate the practical use of the high-density strain sensor array as a multichannel pulse sensing system for monitoring pulses in terms of their spatiotemporal resolution.

Bioactive Metal Ion-Coordinated Dynamic Hydrogel with Antibacterial, Immunomodulatory, and Angiogenic Activities for Infected Wound Repair.

The repair of infected wounds is a complex physiopathologic process. Current studies on infected wound treatment have predominantly focused on infection treatment, while the factors related to delayed healing caused by vascular damage and immune imbalance are commonly overlooked. In this study, an extracellular matrix (ECM)-like dynamic and multifunctional hyaluronic acid (HA) hydrogel with antimicrobial, immunomodulatory, and angiogenic capabilities was designed as wound dressing for the treatment of infected skin wounds. The dynamic network in the hydrogel dressing was based on reversible metal-ligand coordination formed between sulfhydryl groups and bioactive metal ions. In our design, antibacterial silver and immunomodulatory zinc ions were employed to coordinate with sulfhydrylated HA and a vasculogenic peptide. In addition to the desired bioactivities for infected wounds, the hydrogel could also exhibit self-healing and injectable abilities. Animal experiments with infected skin wound models indicated that the hydrogel dressings enabled minimally invasive injection and seamless skin wound covering and then facilitated wound healing by efficient bacterial killing, continuous inflammation inhibition, and improved blood vessel formation. In conclusion, the metal ion-coordinated hydrogels with wound-infection-desired bioactivities and ECM-like dynamic structures represent a class of tissue bionic wound dressings for the treatment of infected and chronic inflammation wounds.

Cellulose nanocomposite tough hydrogels: synergistic self‐healing, adhesive and strain‐sensitive properties

AbstractRecent advancements are notable in electrically conductive hydrogels emulating human skin functions. However, a significant challenge remains: crafting a single conductive gel that integrates self‐healing, robust mechanical strength, and excellent electrical traits. Our innovation lies in a strong, lightweight, curable gel achieved through multiple coordination bonds between cellulose crystals and acid‐treated multi‐walled carbon nanotubes (MWCNTs) in a polymer network. Embedded MWCNTs act as dynamic bridges within a porous structure, giving exceptional mechanical performance. Reversible coordination interactions confer remarkable recovery and reliable mechanical and electrical self‐healing. Additionally, these ionic gels function as adaptable stress sensors, detecting significant movements like finger and joint motions. This work introduces MWCNT‐incorporated nanomaterials with good stretchability, high ion conductivity, remarkable self‐healing nature, and good stress sensitivity. Such proteins hold promise for electronic sensors, wearable devices, and healthcare monitoring, unveiling a path to diverse applications. Our study addresses challenges and unlocks possibilities for materials that can adapt, withstand, and sense in innovative ways. © 2024 Society of Chemical Industry.

Nanocellulose membrane with double-salt deep eutectic solvent for efficient carbon capture

Membrane-based gas separation technology is becoming increasingly attractive as a feasible alternative for carbon capture to alleviate global warming. Here, a double-salt deep eutectic solvent (DES) composed of organic salt (choline chloride) and inorganic salt (ZnCl2) is designed. The as-prepared DES exhibits a superb affinity and compatibility with nanocellulose because of the interactions between salt ions and cellulose carboxyl/hydroxyl groups. Through a solvent impregnation process, the DES was integrated into the nanocellulose gel precursor and used as a facilitated transport agent to form the functionalized nanocellulose membrane. The DES is tightly attached to the cellulose fibers with a high uniformity in the membrane matrix. Gas separation tests demonstrated that the DES@nanocellulose membranes presented a maximum CO2 permeability of 155.8 Barrer, with CO2/N2 and CO2/CH4 ideal selectivities of 43.6 and 48.4, respectively. Mixed gas separation tests were performed and the optimal membrane exhibited separation factors of 48.1 and 52.3 for CO2/N2 and CO2/CH4, respectively. The membranes provide a high solubility for CO2 due to the presence of abundant zinc ions, choline cations and carboxyl groups in the network, which can establish reversible coordination with CO2 and promote CO2 transport.

Hydroxypropyl chitosan/ε-poly-l-lysine based injectable and self-healing hydrogels with antimicrobial and hemostatic activity for wound repair

The biggest obstacle to treating wound healing continues to be the production of simple, inexpensive wound dressings that satisfy the demands associated with full process of repair at the same time. Herein, a series of injectable composite hydrogels were successfully prepared by a one-pot method by utilizing the Schiff base reaction as well as hydrogen bonding forces between hydroxypropyl chitosan (HCS), ε-poly-l-lysine (EPL), and 2,3,4-trihydroxybenzaldehyde (TBA), and multiple cross-links formed by the reversible coordination between iron (III) and pyrogallol moieties. Notably, hydrogel exhibits excellent physicochemical properties, including injectability, self-healing, water retention, and adhesion, which enable to fill irregular wounds for a long period, providing a suitable moist environment for wound healing. Interestingly, the excellent hemostatic properties of the hydrogel can quickly stop bleeding and avoid the serious sequelae of massive blood loss in acute trauma. Moreover, the powerful antimicrobial and antioxidant properties also protect against bacterial infections and reduce inflammation at the wound site, thus promoting healing at all stages of the wound. The study of biohydrogel with multifunctional integration of wound treatment and smart medical treatment is clarified by this line of research.

High mechanical strength, strong adhesion, self-healing and conductive ionic hydrogels for motion detection

The development of conductive hydrogels with outstanding mechanical properties, robust adhesion, and high sensitivity is still a major challenge. This study successfully addresses this issue by a multi-functional ionic conductive hydrogel based on a highly entangled double network (DN) structure with excellent mechanical properties, strong adhesion, high sensitivity and self-healing ability. Polyacrylic acid (PAAc)/chitosan (CS) constructed the Double Network with physical entanglement as the main effective crosslinking. The sliding entanglement points made the hydrogel show a more uniform directional network structure during stretching, and the energy dissipation was greatly reduced. Active chemically reactive polydopamine (PDA), CS, and PAAc are complexed with aluminum ions (Al3+) respectively (building appropriate chemical crosslinking networks), and Al3+ acts as a “bridge” to build a hierarchical porous networks through multiple reversible coordination bond mediated interactions, alternating rigid and elastic domains, thereby improving the comprehensive performance of hydrogels. The tensile strength of PAAc/PDA/CS (ADC) was 173.4 kPa and the elongation at break was 921.9%, both of which were improved simultaneously. Moreover, ADC composite hydrogels exhibit excellent self-healing and adhesion properties, which can be attributed to the rich reversible/irreversible interactions brought about by PDA, with an impressive adhesion strength of 85.2 kPa on pig skin, further enhancing its practicality. Additionally, the ionic hydrogel demonstrates high strain sensitivity to tension, making it an ideal material for stable sensor signal output. The sensitivity coefficient (GF) reaches an impressive 11.24, highlighting the importance of this hydrogel in ensuring consistent and precise data collection. This innovative approach expands the idea and provides data support for the molecular structure design of high-performance wearable hydrogel sensors.

Self‐Healing, Injectable Hydrogel Dressing for Monitoring and Therapy of Diabetic Wound

AbstractChronic diabetic wound repair is a global medical challenge. Developing a hydrogel dressing to effectively promote angiogenesis and detect wound state in diabetic wound management is an unmet medical requirement. Herein, a facile and efficient strategy to prepare self‐healing hydrogel with enhanced angiogenesis and real‐time monitoring for diabetic wounds is presented, by cross‐linking carboxymethyl cellulose (CMC) with precoordinated europium‐ethylenediaminetetraacetic acid (Eu‐EDTA) complexes. Benefiting from the dynamic and reversible coordination interaction formation, the hydrogel exhibits remarkable injectability and self‐healing properties, thus forming efficient coverage in irregular and deep wounds with minimally invasive procedures. Furthermore, the fluorescence of the hydrogel changes linearly with pH value in the range of 4.5–7.5 and enables real‐time pH measurement to monitor the wound state. More importantly, the hydrogel can effectively promote the proliferation and migration of endothelial cells and enhance tube formation ability, demonstrating great angiogenesis capacity in tissue remodeling. The in vivo experiments manifested that the hydrogel can enhance angiogenesis by upregulating the expression of angiogenesis‐related factors and downregulating matrix metalloproteinase‐9 (MMP‐9), contributing to granulation tissue formation, collagen deposition, and diabetic wound repair. This work can provide a promising strategy for diagnosis and therapy in clinical diabetic wounds.

Construction of strain responsive Ti-containing carboxymethyl cellulose hydrogel with transitional coordination precursor

Due to marvelous sensitivity and flexibility, conductive hydrogels are popularly used as strain sensors in intelligent skin and wearable electronic devices fields. However, hydrogel tends to be destroyed after long-term use or in accident, leading to performance degradation. Herein, we developed an environmental-friendly Ti-containing conductive hydrogel. The hydrogel network was constructed via a simple two-step method with coordination reaction and amidation reaction based on a metal ion precursor from transitional coordination. The synergies of reversible metal coordination bonds and dynamic hydrogen bonds endowed the hydrogel with excellent self-healing properties (3 h, 93.66 %), tensile properties (136.46 kPa), compression properties (1.122 MPa), and anti-fatigue performance. At the same time, the hydrogel showed excellent self-adhesion, even underwater. Due to Ti4+, electrical conductivity of the hydrogel was visibly enhanced (σ = 25.64 mS·cm−1), which resulted in fast response (TS [time sensitivity] = 24.78 s−1) and short recovery time (153 ms). As a flexible strain sensor, the hydrogel with stable conductivity and high sensitivity could precisely detect and distinguish a series of human motions, even different letter pronunciations. These remarkable features make it a promising application in the fields of intelligent skin and wearable electronic devices.

A Safe Organic/Inorganic Composite Anode for Sodium‐Ion Batteries

AbstractSodium‐ion batteries (SIBs), based on hard carbon anodes and Na+‐intercalation compound cathodes, have gained significant attention. Nonetheless, hard carbon anodes involve the storage of Na+ at a low potential, typically below 0.1 V (vs Na/Na+), which increases the risk of dendritic Na growth on the anode surface during overcharging. Herein, a safe organic/inorganic composite anode containing tetrasodium 3,4,9,10‐perylenetetracarboxylate (Na4PTC) and Metallic bismuth (Bi) with a weight ratio of 7:2, which exhibits an average potential of 0.7 V (vs Na+/Na) and a capacity of 150 mAh g−1 is proposed. The electrode reaction involves a reversible coordination reaction within the organic host and alloying reactions within the metallic Bi component. Importantly, the organic component efficiently buffers the volume changes in Bi during the alloying reaction, while the metallic Bi enhances the electronic conductivity of the organic material. As a result, this composite anode shows high cycle stability and rate performance, even under high mass loadings ranging from 10 to 50 mg cm−2. Furthermore, it is demonstrated that the Na‐ion full cell, consisting of the composite anode and the Na3V2O2(PO4)2F cathode, exhibits minimal capacity degradation over 100 cycles while maintaining a high areal capacity of 1.1 mA cm−2.

Metal ion-manipulated afterglow on rhodamine 6G derivative-doped room-temperature phosphorescent PVA films.

The long-lived room-temperature phosphorescence (RTP) originating from thiophene boronate polyvinyl alcohol (PVA) has enabled the creation of metal-ion-responsive RTP films doped with spirolactam ring-containing rhodamine 6G (1). In this study, RTP-active PVA films, namely, TDB@PVA and ATB@PVA, were prepared through boronate esterification of thiophene-2,5-diboronic acid (TDB) and 5-acetylthiophene-2-boronic acid (ATB) with the diol units of PVA. The delayed emission properties were evaluated, revealing an emission band at 477nm with a turquoise afterglow for TDB@PVA and at 510nm with a green afterglow for ATB@PVA after UV light irradiation ceased. The photophysical properties were assessed using TD-DFT and DFT calculations at the B3LYP/cc-pVDZ level. N-(rhodamine-6G)lactam dye with a salicylimine unit (1) was doped into the RTP-based PVA films, producing a multicolored afterglow upon the addition of metal ions. This phenomenon is explained by a triplet-to-singlet Förster-type resonance energy transfer process from the cross-linked thiophene boronate in PVA to the metal-ion-activated colored form of 1. This photophysical feature finds applicability in encryption techniques. Notably, the reversible metal-ligand coordination of 1 in the PVA system enabled a write/erase information process.

2 + 2] cycloaddition and its photomechanical effects on 1D coordination polymers with reversible amide bonds and coordination site regulation

Photo-responsive materials can convert light energy into mechanical energy, with great application potential in biomedicine, flexible electronic devices, and bionic systems.