The rational control of ligand substitution in metal complexes remains underexplored for turn-on fluorescent probes. Here, varying the metal center (Co2+, Ni2+, or Cu2+) in AIE-based complexes M(L)2 (L = tetraphenylethylene-based β-diketone) enables precise tuning of metal-ligand bond dissociation, dictating competitive ligand exchange with histidine (His). Single-crystal X-ray diffraction confirmed the structures. All complexes are nonemissive in the aggregated state due to paramagnetic quenching. Upon His addition, only Ni(L)2 undergoes rapid and complete ligand displacement, generating a strong fluorescence turn-on signal within 10 min at room temperature. Co(L)2 reacts much more slowly (>560 min), while Cu(L)2 shows no change. DFT calculations based on crystal structures quantify Gibbs free energy changes: spontaneous displacement in Ni(L)2 correlates with favorable ligand dissociation energetics, whereas Cu(L)2 is thermodynamically trapped. Exploiting this metal-dependent reactivity, Ni(L)2 serves as a highly selective and rapid fluorescent probe for His, discriminating against 20 other amino acids with a detection limit of 4.66 nM. This work establishes a coordination chemistry strategy for designing small-molecule probes by modulating metal-dependent dissociation energetics in AIE complexes, moving beyond conventional PET mechanisms.

Rare earth (RE) ions, characterized by unique 4f electronic configurations and shielded f-f transitions, serve as exceptional optical centers exhibiting narrow-band emission, long-lived luminescence, and rich energy-level structures. The construction of high-performance RE coordination-based photofunctional materials critically relies on the synergistic integration of the "antenna effect", provided by meticulously designed organic ligands, and the distinctive excited-state properties of RE ions. This molecular engineering approach not only maximizes the intrinsic photophysical advantages of RE elements, but also enables the precise tailoring of materials for diverse cutting-edge applications. This review provides a systematic and comprehensive analysis of RE coordination-based photofunctional materials, spanning from fundamental design principles and controllable synthesis strategies to emerging applications. We delve into the structure-activity relationships across various categories, including molecular complexes, supramolecular assemblies, coordination polymers, metal-organic frameworks (MOFs), and RE-covalent-bonded organic frameworks (RE-COFs). Furthermore, we highlight their transformative roles in optoelectronics, advanced anti-counterfeiting, biomedical imaging/therapy, radiation detection (scintillators) and photochemical catalysis. Finally, we outline current challenges and future perspectives, aiming to inspire interdisciplinary innovation and accelerate the commercialization of next-generation RE molecular photonic materials.

Organic room-temperature phosphorescence (RTP) materials have emerged as promising candidates for advanced photonic applications. However, achieving precise control over phosphorescence lifetime and integrating multiple emission modes within a single system remain major challenges. Herein, we report a strategy to fabricate tunable RTP materials by covalently incorporating a vinyl-functionalized Eu3+ complex into a polyacrylamide backbone that also contains organic phosphor units (phenylpyridinium derivatives). The Eu3+ complex serves a dual role: as a structural node, it coordinates with polymer chains to form a crosslinked network, enhancing matrix rigidity and effectively suppressing non-radiative transitions, which prolongs the RTP lifetime from 0.81 s to 1.63 s. Simultaneously, it acts as an energy acceptor, enabling a ligand-to-metal photosensitized energy transfer (PSET) process from the organic phosphors to Eu3+ ions. By simply adjusting the doping concentration of the Eu3+ complex, we achieve continuous modulation of the RTP lifetime (from 0.81 s up to 1.63 s, and then down to 0.16 s) and the afterglow duration has also been extended (from 7.0 s up to 21.0 s, and then down to 13.0 s). Intriguingly, we realize a unique dual-emissive system featuring long-wavelength (red) luminescence from Eu3+ and short-wavelength (green) ultralong phosphorescence. This finely manipulated optical behavior, encompassing both color and lifetime dimensions, is leveraged to construct a high-security-level, multi-layer information encryption platform based on time-resolved and color-resolved dot-matrix patterns. This work not only provides a facile and robust method for dynamically manipulating RTP properties but also opens new avenues for designing smart luminescent materials for cutting-edge anti-counterfeiting and information storage technologies.

Luminescent rare earth (RE) complex assemblies hold broad application prospects in bioimaging, information encryption, white-light illumination, and scintillators, owing to their unique photophysical properties, such as long luminescence lifetimes, sharp line-like emissions, large pseudo-Stokes shifts, and multi-stimuli responsiveness. Achieving highly ordered structures and precise functionalization relies crucially on the synergistic regulation of ligand engineering and assembly strategies. Rational ligand design not only enables efficient sensitization of RE luminescence but also incorporates intermolecular interactions that drive assembly. Concurrently, precise control over assembly processes, including dynamic, co-, and hierarchical assembly, allows the construction of micro/nano materials with complex architectures and emergent functionalities, thereby overcoming inherent limitations of RE complexes in stability, solubility, and processability. This review systematically summarizes recent advances in assembled materials based on luminescent RE complexes, with a focus on ligand design principles, diverse assembly strategies, and their regulatory mechanisms on luminescence behavior. Structure–property relationships in these assemblies are thoroughly discussed, and future challenges and opportunities in this field are outlined.

Electron transfer process (ETP) represents an efficient and robust pathway in peroxymonosulfate (PMS) activation, yet its practical application is limited by sluggish kinetics, inefficient electron transport, and constrained catalyst suitability. Herein, we design a roselike Ce-doped Co3O4 catalyst (RL Ce-Co3O4) with electron-deficient Co sites to enable efficient PMS activation by a selective ETP pathway in spinel oxide. Atomic-level Ce incorporation in Co3O4 induces electron delocalization of octahedral cobalt (CoOh) via 3d-2p-4f coupling orbital, constructing electron-deficient CoOh active sites with depopulated 3d orbitals. The roselike architecture improves the accessibility of active sites to further promote the reaction kinetics. Mechanistic insight reveals that the electron-deficient CoOh sites enhance the adsorption and stabilization towards both PMS and bisphenol A (BPA) by intensified Co-O covalent interactions. Meanwhile, Ce doping improves the electrical conductivity of Co3O4, promoting rapid electron transfer from BPA to PMS* via a catalyst bridge, thereby disrupting the conventional Co2+/Co3+ redox cycling and establishing a catalyst-mediated ETP pathway. Synergistically, RL Ce-Co3O4 exhibits superior performance, achieving 99.9

Water-stable Tb-MOF detects uranyl via fluorescence quenching, with intensity/lifetime readouts and 14 nM LOD in seawater. Smartphone-assisted strips enable robust instrument-free on-site monitoring.

The concentration of uranyl ions (UO22+) is a key indicator for environmental surveillance and water-safety assessment after nuclear radiation incidents, yet its on-site, real-time, and reliable detection in complex waters with high salinity and strong interference remains challenging. Fluorescence-lifetime readout offers improved robustness and anti-interference capability over intensity-only sensing, but lifetime-responsive strategies for UO22+ are rarely reported. Herein, we present ZJU-168, an aqueous-stable metal-organic framework (MOF), enabling dual-readout sensing of UO22+via fluorescence intensity and lifetime. ZJU-168 exhibits rapid luminescence quenching and a pronounced lifetime shortening upon exposure to UO22+, arising from a synergistic quenching mechanism involving inner filter effect (IFE) and photoinduced electron transfer (PET). As a result, ZJU-168 achieves ultrasensitive detection with a detection limit of 17 nM in pure water and 14 nM in seawater, both below the U.S. Environmental Protection Agency limit for uranium in drinking water (130 nM). Moreover, ZJU-168 immobilized on filter paper, coupled with smartphone RGB analysis, enables rapid, portable, and instrument-free on-site visual detection. Overall, this work provides a stable and field-deployable strategy for real-time monitoring of UO22+ in complex aquatic environments.

The sluggish kinetics in charge transfer and rapid recombination of photogenerated carriers severely limit the efficiency of photocatalytic hydrogen production. While S-scheme heterojunction offers a promising solution, the efficiency of interfacial charge transfer is frequently impeded by disordered structures and thermodynamic instability at conventional heterojunction interfaces. Herein, we propose a ligand-mediated interfacial engineering strategy to construct S-scheme heterojunction photocatalyst (ZnCdS/TiO2) featuring oxygen-bridged interfaces. By employing ethylene glycol as a molecular "solder" during the synthesis process, a dynamic ligand exchange process stabilizes a non-equilibrium hydroxylated surface configuration and establishes robust interfacial oxygen bridges between ZnCdS nanodots and TiO2 nanoflowers. Combined experimental and theoretical studies reveal that the engineered interface optimizes the electronic structure and establishes high-speed charge-transport channels, thereby achieving directional separation of electrons and holes with minimized recombination. The optimized heterojunction photocatalyst achieves a hydrogen evolution rate of 30.98 mmol center dot g-1 center dot h-1, which is 3.57 and 1.84 times higher than that of pristine ZnCdS and a counterpart heterojunction lacking oxygen bridges, respectively. And it surpasses most reported heterojunction photocatalysts. This work emphasizes the pivotal function of ligand chemistry in designing heterojunction interfaces for advancing efficient photocatalytic energy conversion.

Enabled by excellent biocompatibility and functional designability, hydrophilic flexible functional materials are gaining traction in fields like flexible electronics and implantable/interventional medical devices. Silicone rubber (SR), as a conventional high-performance material, exhibits outstanding flexibility, fatigue resistance, and biocompatibility, making it an ideal substrate for constructing such functional materials. However, its inherent hydrophobicity and low surface energy severely limit compatibility with polar modifiers and hinder further functionalization. To address this, we developed a universal in situ modification strategy based on a "gradient polarity modification" concept. By establishing a polarity transition ladder between SR and strongly polar hydrophilic materials (e.g., quaternary ammonium and zwitterionic compounds), this method successfully achieves a hydrophilic interdigitated SR network and enables modification from the surface to the bulk. The resulting materials exhibit a combination of superior properties, including persistent bulk hydrophilicity, remarkable aqueous lubrication, and maintained mechanical robustness. By demonstrating the successful fabrication of a lubricative/antibacterial catheter and a long-lasting lubrication meniscus, this strategy proves to be highly designable in function and directly applicable for modifying pre-formed SR devices. Its exceptional responsiveness, as confirmed by motion capture, underscores a significant potential for use in advanced sensing applications.

ABSTRACT Integrating achiral luminophores into chiral supramolecular helices represents a promising route to strong circularly polarized luminescence (CPL). However, for lanthanide systems, efficient emitter loading and effective chirality induction remain challenging due to weak host–guest interactions and the shielded nature of 4f electrons. Herein, we report a supramolecular chelation strategy that implants Eu 3+ emitters into pre‑assembled helical nanoribbons (HNRs), enabling efficient chirality induction and tunable CPL brightness. Two cholesterol–terpyridine conjugates, differing only in their linker chemistry (ester vs. carbonate), demonstrate that the ester linker promotes long‑range chirality induction and HNR formation, whereas the carbonate counterpart yields achiral aggregates. Moreover, the assembly sequence is crucial: pre‑formation of the helical scaffold preserves the non‑covalent network necessary for effective chirality induction, whereas prior metal coordination introduces steric hindrance that disrupts chiral order. The resulting systems exhibit orthogonal luminescence responses: Eu 3+ ‑loaded assemblies are humidity‑sensitive but thermally stable, while β ‑diketonate‑shielded analogues are temperature‑responsive yet humidity‑resistant, allowing multi‑level information encryption. By introducing this modular “assemble‑then‑coordinate” approach, we provide new insights into supramolecular chirality induction and open avenues toward advanced, stimulus‑responsive CPL materials.

This article reviews recent progress in the field of rare earth molecule-based functional materials in 2025,focusing on the latest breakthroughs in ligand engineering,controlled assembly and functional regulation covering luminescent,magnetic,catalytic,and multifunctional coupled systems.The aim is to provide an overview of research spanning molecular design to device-level applications,investigate function-oriented molecular engineering and performance regulation,analyze common scientific challenges in the field,and propose solutions for the targeted design and industrial application of materials.

The dual challenges of energy shortages and environmental pollution necessitate innovative solutions, particularly in hydrogen energy production and photocatalytic degradation of pollutants. This study explored a novel Ce3+-doped ZnIn2S4 photocatalyst, engineered through vacancy modulation to enhance photocatalytic properties. Utilizing a one-step soft template method, we precisely adjusted the S vacancy content by varying the thioacetamide ratio, resulting in the optimized Ce-Sv-ZnIn2S4 catalyst, CZISv-M. Characterization techniques, including in-situ X-ray photoelectron spectroscopy (in-situ XPS), femtosecond transient absorption spectroscopy (fs-TAS), and density functional theory (DFT) calculations, revealed the trapping effect of S vacancy and Ce3+ to capture electrons and holes, respectively. This synergistic interplay between Ce3+ and S vacancies established an effective charge-carrier transfer pathway, achieving the efficient carrier separation. Moreover, the charge extraction effect of Ce3+ further enhanced the electron trapping effect of S vacancy, which accelerated the charge transfer and optimized migration dynamics. The CZISv-M obtained remarkable hydrogen evolution rate of 8.79 mmol g- 1 h- 1 and 93 % degradation of tetracycline hydrochloride. Our findings highlight the potential of Ce3+-doped ZnIn2S4 with engineered vacancies as a promising candidate for advanced photocatalytic applications, offering valuable insights into the development of next-generation defect-engineered photocatalysts.

Counterfeiting presents severe global economic and safety threats, driving demand for advanced anti-counterfeiting solutions. While CsPbBr3 perovskite nanocrystals (NCs) offer exceptional optical encoding properties, their application is limited by intrinsic instability and single-mode emission. This work introduces a tripodal quaternary ammonium-functionalized Yb3+ complex ([YbL3]3+) as a "molecular adhesive" to simultaneously address these constraints. The complex directs CsPbBr3 NC self-assembly into ordered 3D cubic superstructures (Yb-CsPbBr3 SNCs) via ionic interactions while passivating surface defects. Resultant Yb-CsPbBr3 SNCs exhibit three critical advances: 1) Dual-mode luminescence (519 nm NC green emission; 980 nm Yb3+ NIR emission) enabling covert authentication; 2) Significantly enhanced environmental stability, particularly against water and heat; 3) Intrinsic microscale assembly randomness permitting physically unclonable function (PUFs) generation for high-security encryption. Exploiting differential NIR emission, thermal stability, and humidity sensitivity between Yb-CsPbBr3 SNCs and CsPbBr3 NC, a multi-stimuli-responsive (NIR/thermal/humidity) anti-counterfeiting platform is demonstrated with flexible "one-time" or "repeated" decryption. Stochastic assembly further enables high-capacity PUFs exhibiting validated randomness, uniqueness, and similarity index. This Yb3+-complex-mediated assembly strategy overcomes perovskite NC stability and encoding limitations, unlocking dual-mode luminescence and unclonable security features to establish a versatile platform for next-generation anti-counterfeiting and optical encryption.

Metallic foams hold significant promise as lightweight structural materials. However, most conventional metallic foams are inherently rigid and brittle, frequently undergoing structural collapse. There is an urgent demand to develop cost-effective, facile-to-synthesize metallic foams with enhanced flexibility. Herein, it is discovered that diethanolamine solvent, a multifunctional organic solvent, not only reduces Ni2+ ions but also induces the assembly of generated Ni0 units into 3D metallic nickel (Ni-BPHs) sponges. In addition, the optimization of the binary solvent ratio combined with an acetic acid-assisted method is demonstrated to markedly accelerate the reaction kinetics, concomitant with significantly enhance the coordination density of organic ligands on metallic nickel surface. This approach enables the synthesis of metallic nickel (Ni-BNSs) sponges with enhanced flexibility. The Ni-BPHs and Ni-BNSs as electrocatalysts that exhibit efficient activity and stability for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media. The solvent-ligand-mediated reduction and induced assembly strategy has also been demonstrated by extending to other similar ligands. This work marks an important advance in metallic nickel foams and provides a promising strategy for synthesizing mechanically flexible metallic sponges.

Counterfeiting presents severe global economic and safety threats, driving demand for advanced anti‐counterfeiting solutions. While CsPbBr 3 perovskite nanocrystals (NCs) offer exceptional optical encoding properties, their application is limited by intrinsic instability and single‐mode emission. This work introduces a tripodal quaternary ammonium‐functionalized Yb 3+ complex ([YbL 3 ] 3+ ) as a “molecular adhesive” to simultaneously address these constraints. The complex directs CsPbBr 3 NC self‐assembly into ordered 3D cubic superstructures (Yb‐CsPbBr 3 SNCs) via ionic interactions while passivating surface defects. Resultant Yb‐CsPbBr 3 SNCs exhibit three critical advances: 1) Dual‐mode luminescence (519 nm NC green emission; 980 nm Yb 3+ NIR emission) enabling covert authentication; 2) Significantly enhanced environmental stability, particularly against water and heat; 3) Intrinsic microscale assembly randomness permitting physically unclonable function (PUFs) generation for high‐security encryption. Exploiting differential NIR emission, thermal stability, and humidity sensitivity between Yb‐CsPbBr 3 SNCs and CsPbBr 3 NC, a multi‐stimuli‐responsive (NIR/thermal/humidity) anti‐counterfeiting platform is demonstrated with flexible “one‐time” or “repeated” decryption. Stochastic assembly further enables high‐capacity PUFs exhibiting validated randomness, uniqueness, and similarity index. This Yb 3+ ‐complex‐mediated assembly strategy overcomes perovskite NC stability and encoding limitations, unlocking dual‐mode luminescence and unclonable security features to establish a versatile platform for next‐generation anti‐counterfeiting and optical encryption.

Heterogeneous precious metal catalysts are prone to agglomeration during preparation, requiring high usage with consequently high costs. Maximizing the efficiency of precious-metal utilization is of great significance in the design of supported precious metal catalysts. Herein, 2,2'-bipyridyl-5,5'-dicarboxylic acid was used as the ligand in constructing the UiO-67-Ce-BPyDC framework with Ce4+ coordination. This framework enables precise adsorption and coordination of Pd2+ at the nitrogen sites of pyridine, promoting high dispersion of the Pd species at a single site, thereby facilitating controlled palladium loading. This precursor was used to fabricate supported Pd-based catalysts on CeO2 (Pd-N/CeO2-P) via pyrolysis. Notably, because the Pd species are homogeneously distributed on CeO2 with strong interactions, Pd-N/CeO2-P exhibits remarkable efficiency in cleaving the C−O bonds of diphenyl ether (DPE) to produce cyclohexanol, with a selectivity of 72.1%. The origin of the high selectivity of cyclohexanol is further elucidated using theoretical calculations; that is, DPE undergoes not only hydrogenolysis on Pd-N/CeO2-P, but also hydrolysis to produce more cyclohexanol. This study not only demonstrates a successful strategy for designing highly dispersed metal catalysts, but also underscores the importance of such tailored catalysts in the advancement of sustainable lignin depolymerization technologies.

Biological encapsulants, such as viral capsids and ferritin protein cages, use many identical subunits to tile the surface of a polyhedron. Inspired by these natural systems, synthetic chemists have prepared an extensive series of artificial nanocages, with well-defined shapes and cavities. Rational control over the self-assembly of discrete, nanometre-scale, hollow coordination cages composed of simple components still poses considerable challenges as a result of the entropic costs associated with binding many subunits together, difficulties in the error-correction processes associated with assembly, and increasing surface energy as their size grows. Here we demonstrate the construction of a family of nanocages of increasing size derived from a single simple pentatopic pyrrole-based subcomponent. Reasoned shifts in the preferred coordination number of the metal ions employed, along with the denticity and steric hindrance of the ligands, enabled the generation of progressively larger cages, incorporating more subunits. These structural changes of the cages through these ‘mutations’ are reminiscent of differences in the folding of proteins caused by minor variations in their amino acid sequences; understanding how they impact capsule structure and thus cavity size may help to elucidate construction principles for still larger, more complex and functional capsules, capable of binding and carrying large biomolecules as cargoes.

A lanthanide-based metal-organic framework Eu0.52Tb0.48-TCPP was synthesized under solvothermal condi- tions, where H4TCPP=4,4',4 '',4"-(pyrazine-2,3,5,6-tetrayl)-tetrabenzoic acid. The structure and composition were characterized by powder X-ray diffraction, thermogravimetric analysis, infrared spectroscope, and elemental analy- sis. Eu0.52Tb0.48-TCPP showed excellent chemical stability, thermal stability, and good fluorescence sensing perfor- mance, which realized efficient and sensitive detection of 2, 4, 6-trinitrophenol (TNP). The detection limit was 0.49 mu molL-1. In addition, the fluorescence sensing mechanism of TNP detected by Eu0.52Tb0.48-TCPP was explored and a portable fluorescence test papers and composite films were successfully prepared for the real - time and on - site inspection of TNP.

Covalent organic frameworks (COFs) are promising materials for photocatalytic hydrogen peroxide (H2O2) production. However, optimizing their electronic structures to enhance charge separation, oxygen adsorption, and reaction efficiency remains a challenge. Here we show that incorporating thiophene and furan isomeric units into the side chains of COFs enables precise tuning of their electronic structures and photocatalytic activity. Thiophene-containing frameworks exhibit superior charge separation and photocatalytic performance compared to those with furan, owing to stronger donor-acceptor interactions. A 2-substituted thiophene-based COF (DT2TA-TAPB), synthesized from 1,3,5-tris(4-aminophenyl)benzene and 2,5-di(thiophen-2-yl)terephthalaldehyde, exhibits reduced exciton binding energy, extended electron lifetime, and improved spatial charge separation. Mechanistic analysis reveals that the sulfur and adjacent carbon atoms within the thiophene of DT2TA-TAPB stabilize the endoperoxide intermediate, promoting a one-step, two-electron pathway for H2O2 generation. Consequently, DT2TA-TAPB achieves H2O2 yields of 10972 and 8587 μmol g-1 h-1 in 10% ethanol and pure water, respectively, outperforming most reported COF-based photocatalysts.

ConspectusRare earth (RE) elements, due to their unique electronic structures, exhibit excellent optical, electrical, and magnetic properties and thus have found widespread applications in the fields of electronics, optics, and biomedicine. A significant advancement in the use of RE elements is the formation of RE complexes. RE complexes, created by the coordination of RE ions with organic ligands, not only offer high molecular design flexibility but also incorporate features such as a broad absorption band and efficient energy transfer of organic ligands. Through the "antenna effect", organic ligands can transfer energy to RE ions, enhancing their luminescence efficiency. Moreover, the modification of the ligands can influence the local environment of the RE ions, thereby regulating their electronic structures and energy-level distributions. This makes it one of the important avenues for the efficient development and utilization of RE resources.The meticulous design of organic ligands during molecular synthesis enables the precise construction and regulation of RE complex structures, which are essential for probing molecular-level structure-performance relations and developing functional materials in fields such as optoelectronics, sensing, and catalysis/energy. Despite notable advancements, challenges persist in refining synthesis methodologies, innovating RE complex-based materials, enhancing stability, gaining better control over device functionality, and realizing high-value applications. This Account summarizes the recent advancements in molecular design and performance regulation achieved by our research group, particularly focusing on the synthesis and functional regulation of RE complex-based materials. We have employed strategies such as coordination self-assembly, in situ coordination, and microstructural evolution to achieve the precise synthesis and functional modulation of RE complex-based materials. These approaches have allowed us to finely tune properties such as the luminescence, electrical performance, and catalytic performance of various material systems. Consequently, we have made considerable strides in multidimensional optical information storage, the development of intelligent biological probes, the preparation of nanocatalysts, and the enhancement of inorganic-organic hybrid perovskite solar cell devices. Finally, we are committed to conducting an in-depth analysis of the challenges and opportunities that arise from the precise synthesis methods, performance regulation strategies, and innovative applications of RE complex-based functional materials. Additionally, we aim to propose potential solutions to current issues. This Account comprehensively summarizes the developments in RE complex-based materials to stimulate innovative thinking and new research directions and to establish a foundation for function-oriented precise synthesis methods.