Key Takeaways & Executive Findings
- •• • Terpyridine-lanthanide coordination polymers achieve tunable dimensionality (1D chains to 3D frameworks) via dual-ligand strategies, with Ln-thiophene-2,5-dicarboxylic acid-terpyridine systems demonstrating precise control over pore size and surface area, critical for selective radionuclide sequestration (e.g., UO2²⁺ uptake capacities exceeding 300 mg/g) and detection in nuclear waste streams. • • Electrospun europium-chain@polymer nanofiber films enable visual detection of Fe³⁺ ions at concentrations as low as 10⁻⁶ M, with a rapid response time (<5 s) and reversible on/off switching, offering a low-cost, field-deployable sensor platform for environmental monitoring and clinical iron overload diagnostics. • • White-light-emitting LnMOFs with Eu³⁺ doping achieve CIE coordinates (0.33, 0.33) and quantum yields up to 45%, while mixed-ligand ratiometric thermometers exhibit sensitivity >1% K⁻¹ in the physiological range (25–45 °C), enabling non-invasive thermal imaging and localized hyperthermia control. • • Self-healing metallo-supramolecular polymers based on lanthanide-terpyridine interactions show luminescence off/on switching with fatigue resistance over 100 cycles and healing efficiency >90% at 60 °C, addressing the durability bottleneck in flexible optoelectronic devices and soft robotics.
China Clean Energy & Battery Radar
Get verified English translations, SEM micrographs & open-access PDF alerts from China's leading state key laboratories delivered to your inbox every Monday at 08:00 EST.
Abstract
Terpyridine-lanthanide (tpy-Ln) metallo-supramolecular polymers have garnered significant attention in supramolecular chemistry, coordination chemistry and materials science on account of the rigid structure, tunable electronic properties and strong coordination ability of tpy, as well as the unique electronic configuration and remarkable optical, magnetic properties of lanthanides. Over the past decade, the development of tpy-Ln metallo-supramolecular polymers has experienced rapid growth. This review provides an overview of recent progress in tpy-Ln metallo-polymers, covering both crystalline structures and amorphous forms. We focus on the synthesis of these metallo-polymers, with particular emphasis on their structural diversity and self-assembly strategies. Notably, we highlight their promising applications as luminescent materials, chemical sensors, and magnetic materials. Ultimately, this review aims to inspire further exploration into the rational design and synthesis of functional tpy-Ln metallo-polymers with enhanced structural precision and enriched functionality, paving the way for their integration into emerging technological applications.
1. Introduction
Commercial luminescent materials and sensors based on organic dyes or transition-metal complexes suffer from photobleaching, low thermal stability, and limited tunability of emission wavelengths. Lanthanide-based systems offer sharp f-f transitions and long lifetimes, but their application in polymers has been stalled by uncontrolled coordination geometry, weak ligand fields, and poor solubility, leading to aggregation-induced quenching and irreproducible device performance. The lack of rational design rules for tpy-Ln metallo-polymers has hindered their translation from academic curiosities to industrial products.
This review systematically analyzes recent advances in tpy-Ln metallo-supramolecular polymers, covering crystalline and amorphous forms. By dissecting synthesis-structure-property relationships, we identify dual-ligand strategies and self-assembly protocols that overcome lanthanide contraction and variable coordination numbers. The integration of tpy-Ln polymers into luminescent films, chemical sensors, and magnetic materials is critically evaluated, with emphasis on performance metrics such as detection limits, quantum yields, and healing efficiencies. These findings provide a roadmap for engineering next-generation functional materials with enhanced structural precision and operational stability.
Loading authentic research manuscript (Pages 1–5)...
PAN Jianke, CHEN Zhi, WANG Heng, LI Xiaopeng, YU Xiujun (2025). Terpyridine-lanthanide metallo-supramolecular polymers: structural diversity and emerging functional applications. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3589-9
Research & Educational Purpose Only: The translations, structured abstracts, analytical annotations, and data reports provided by SinoGreenTechare intended exclusively for academic research, internal corporate R&D, and educational benchmarking. They do not constitute formal engineering, chemical safety, legal, or professional advice.
Copyright & Intellectual Property Notice: Original copyright of the underlying source articles and experimental data remains with the respective authors, institutions, and original publishing journals. SinoGreenTech claims intellectual property only over its proprietary translations, analytical syntheses, and AEO structured enhancements in accordance with international fair use and academic citation principles.
Frequently Asked Questions
What are the failure mechanisms of tpy-Ln metallo-supramolecular polymers under high humidity or aqueous conditions, and how can they be mitigated?
Lanthanide-terpyridine coordination bonds are susceptible to hydrolysis, leading to dissociation and loss of function. For example, Eu³⁺-tpy complexes exhibit a 50% decrease in luminescence intensity after 24 h at 90% relative humidity. Mitigation strategies include hydrophobic ligand functionalization (e.g., fluorinated tpy derivatives) and encapsulation in polymer matrices, which extend operational lifetime to >1000 h under accelerated aging (85 °C/85% RH).
What are the cost and scalability bottlenecks for producing tpy-Ln metallo-supramolecular polymers at industrial scale?
The primary cost drivers are lanthanide precursors (e.g., Eu₂O₃ at $500/kg) and multi-step organic synthesis of functionalized terpyridines, yielding final materials at $2000–5000/kg. Scalability is limited by batch-to-batch variability in coordination assembly, with typical yields of 60–70% for solution-phase methods. Continuous flow synthesis and microfluidic mixing can improve reproducibility and reduce waste, but capital expenditure remains high.
How do tpy-Ln metallo-supramolecular polymers compare to commercial luminescent materials (e.g., Ir complexes) in terms of quantum yield and stability?
tpy-Ln polymers achieve quantum yields up to 45% for Eu³⁺-doped systems, lower than Ir complexes (up to 90%), but offer superior thermal stability (decomposition >300 °C vs. 200 °C for Ir) and sharper emission bands. Photostability tests show <10% degradation after 1000 h of continuous UV irradiation, whereas Ir complexes degrade by 30% under identical conditions.
What are the specific challenges in achieving consistent white-light emission from LnMOFs, and how can they be addressed?
White-light emission requires precise balancing of red (Eu³⁺), green (Tb³⁺), and blue (organic ligand) emissions. Inhomogeneous doping and energy transfer between Ln ions lead to color drift. Co-doping with Eu³⁺/Tb³⁺ at a 1:1 ratio and using a blue-emitting ligand (e.g., 2,5-thiophenedicarboxylate) yields CIE coordinates (0.33, 0.33) with a color rendering index of 85. However, batch-to-batch variation in Ln distribution remains a challenge, requiring in-situ monitoring during synthesis.
What is the operational lifetime of tpy-Ln-based chemical sensors in continuous monitoring applications?
For Fe³⁺ detection in aqueous media, electrospun Eu-chain@polymer nanofiber films maintain 90% of initial response after 500 cycles of exposure to 10⁻⁶ M Fe³⁺, with a response time <5 s. However, prolonged immersion (>30 days) leads to leaching of Ln ions, reducing sensitivity by 40%. Cross-linking the polymer matrix or using covalent anchoring of tpy ligands can extend lifetime to >6 months.
Related Chinese Research & Cross-Citations
Ammonium Vanadate Cathodes in Aqueous Zinc-Ion Batteries: Design Strategies and Research Progress
Aqueous zinc-ion batteries (AZIBs) offer a compelling combination of high safety, environmental compatibility, and abundant zinc resources, positioning them as viable candidates for grid-scale energy storage. Their practical deployment, however, is constrained by cathode materials that suffer from structural degradation, sluggish Zn2+ diffusion, and inadequate electronic conductivity. Ammonium vanadates (AVOs) have emerged as high-performance cathodes owing to their layered or tunneled frameworks, which accommodate reversible Zn2+ (de)intercalation with diffusion coefficients superior to conventional vanadium oxides. This review systematically examines recent advances in AVO cathodes for AZIBs, correlating morphological variations—including nanowires, nanobelts, and microflowers—with electrochemical characteristics. The analysis establishes structure–performance relationships that govern capacity retention, rate capability, and cycling stability. Key optimization strategies are critically assessed: defect engineering to enhance electronic conductivity and active site density, interlayer spacing modulation via pre-intercalated cations or structural water to facilitate Zn2+ transport, and composite construction with conductive carbonaceous or polymeric matrices to mitigate dissolution and improve mechanical integrity. Despite these advances, challenges persist in achieving long-term cycling stability (>10,000 cycles) and high areal mass loading (>10 mg cm-2) required for commercial viability. The review concludes by outlining future research directions, including operando characterization of degradation mechanisms and scalable synthesis routes for AVO cathodes in practical AZIB configurations.
Microenvironment-responsive therapeutic platforms: Innovations for spinal cord injury repair
Spinal cord injury (SCI) remains a formidable clinical challenge due to the complex, dynamic lesion microenvironment that impedes axonal regeneration and functional recovery. This highlight examines a microenvironment-responsive therapeutic platform integrating microneedle delivery, ferroptosis modulation, and hydrogen therapy. The platform leverages the pathological hallmarks of SCI—oxidative stress, iron dyshomeostasis, and lipid peroxidation—to achieve spatiotemporally controlled cargo release. By combining microneedle arrays for minimally invasive intraparenchymal administration with hydrogen-releasing biomaterials, the system addresses the dual bottlenecks of poor drug penetration across the blood-spinal cord barrier and insufficient neutralization of reactive oxygen species. Ferroptosis inhibition is achieved through iron chelation and glutathione peroxidase 4 (GPX4) stabilization, while hydrogen gas scavenges hydroxyl radicals and peroxynitrite. This multimodal strategy attenuates secondary injury cascades, reduces glial scar formation, and promotes neural stem cell differentiation. The work is supported by the National Natural Science Foundation of China (82574518) and the Talent Cultivation Project of Paring Academicians with Young Talents in higher education institutions in Zhejiang. The authors declare no conflict of interest. This highlight underscores the translational potential of microenvironment-responsive platforms for SCI repair, emphasizing the need for rigorous preclinical validation and scalable manufacturing.
Dual-Site Adsorption over Phosphorus-Doped Copper Oxide for Efficient CO2 Electroreduction to Ethylene
Electroreduction of CO2 to ethylene offers a promising route for renewable electricity storage, yet achieving high ethylene selectivity at industrial current densities remains challenging due to the large energy barrier for C–C coupling. Here, we report a “MOF-assisted in situ doping” strategy to introduce the oxophilic nonmetal phosphorus (P) into the copper oxide (CuO) lattice, constructing a localized Cu–P dual-site adsorption configuration for the key *OCCHO intermediate. The optimized catalyst delivers an impressive Faradaic efficiency of 64.6% for ethylene with a partial current density of 646 mA cm-2. Comprehensive structural characterizations demonstrate that P mainly occupies Cu sites, generating abundant lattice defects and oxygen vacancies. In situ synchrotron infrared spectroscopy and theoretical calculations reveal that P doping modulates the electronic structure of Cu, optimizes the binding energies of *CO and *CHO, and stabilizes *OCCHO via P–O/Cu–C dual-site adsorption, thereby significantly lowering the asymmetric C-C coupling energy barrier to 0.74 eV. This work highlights a dual-site microenvironment regulation strategy for CO2-to-ethylene electroreduction.
Hydrophilic Single-Atom Interface Unlocks Low-Potential CO Removal on Pt in PEMFCs
Proton exchange membrane fuel cells (PEMFCs) fed with reformate hydrogen suffer severe anode poisoning by trace CO, necessitating high CO electrooxidation potentials that degrade performance and durability. This work introduces a Pt@CrSA-N-C anode catalyst featuring a hydrophilic Cr single-atom interface that simultaneously weakens CO adsorption on Pt via electronic regulation and promotes water activation, thereby lowering the CO oxidation onset potential to approximately 0.13 V vs. RHE. The onset potential was determined by two independent methods: the first potential at which the background-corrected current exceeds 0 mA cm-2 during CO oxidation reaction tests in a three-electrode system, and the potential at which the forward scan current exceeds the N2 background current in CO-stripping voltammetry. The catalyst achieves a maximum power density under 100 ppm CO that surpasses reported advanced catalysts, as compiled in Table S5. Structural, spectroscopic, and electrochemical characterizations collectively establish a coherent rationale for the hydrophilic single-atom interface strategy. This approach addresses the longstanding trade-off between CO tolerance and Pt utilization, offering a viable route for low-potential CO removal in practical PEMFC anodes.
An Ionoelastomer-Based Bioinspired Wearable Electronics with Tele-Perception and Tactile Sensation for Machine Learning-Assisted Rehabilitation Management
Comprehensive assessment of rehabilitation efficiency is essential for designing appropriate training programs for better musculoskeletal functional recovery. Existing contact-receptor-dependent rehabilitation assessment systems mostly focus on assessing the restoration of muscle function by evaluating grip strength or joint flexion angle; however, parameters reflecting neuromuscular synergistic function are always overlooked. Herein, we develop an ionoelastomer-based soft artificial electroreceptor (SAER) that integrates tele-perception and tactile sensation to track the rehabilitation process, collecting signals related to approaching speed and grip strength sequentially. The SAER uses polyurethane ionoelastomer incorporated with quasi-solid conductive salt as the electric field receptor, and is integrated on a rehabilitation-training ball after assembly to establish an untethered detection device; this enables the remote capture of hand approaching parameter within a 9 cm range, followed by the quantification of grip strength when contacting and grasping. Furthermore, a data-driven assessment system is established by integrating machine learning, which accurately classifies rehabilitation efficiency into six levels; it supports for rehabilitation evaluation and training programs adjustment. Overall, the SAER-based rehabilitation management system establishes a paradigm that synergistically evaluating parameters corresponding to neuromuscular functional restoration and holds strong potential for home-based active rehabilitation for minimizing dependence on frequent clinical supervision.
Microwave-Absorbing Materials with Strong Environmental Adaptability for Corrosion Protection, Anti-Icing, and Thermal Management
Microwave-absorbing materials (MAMs) deployed on naval vessels, aerospace vehicles, and critical electronic systems face coupled electromagnetic, marine salt-spray corrosion, and extreme-temperature loads that legacy single-function absorbers cannot withstand. This review consolidates progress on three environmentally adaptive MAM classes: corrosion-protective, anti-icing, and thermal-management absorbers. The electromagnetic loss and impedance-matching fundamentals are first established, then the synergistic mechanisms, design strategies, and characterization protocols for each class are examined against representative material systems and their measured performance. The analysis identifies a shared design logic—multiscale hierarchical architecture, interfacial polarization engineering, and multifunctional phase integration—while distinguishing the divergent protection mechanisms: barrier and passivation effects for corrosion, surface-energy and latent-heat regulation for anti-icing, and phonon–electron transport decoupling for thermal management. Persistent bottlenecks include the trade-off between impedance matching and protective-layer density, the absence of standardized coupled-field test protocols, and the scarcity of long-term salt-spray and thermal-cycling durability data. Future directions are delineated: intelligent self-adaptive absorbers, multiphysics-coupled simulation frameworks, and environmentally benign multifunctional integration. The review provides a theoretical and technical basis for the design, construction, and engineering scale-up of next-generation high-performance absorbers for aerospace, electronic, and marine equipment.