Polycatenane gels have attracted extensive attention due to their high degree of freedom and mobility. However, the syntheses of poly[2]catenane gels reported to date all rely on the polymer as the backbone. Herein, we prepared poly[2]catenane gels based on entirely sequential assembly of small molecules. Monomer M1 with two unclosed rings was first prepared, which self-assembled to form supramolecular polymers (SPs) via hydrogen bonding and π-π interactions. Upon adding small molecule monomers M2 and M3 with aldehyde groups, ring closing of SPs occurred because the amino groups in the SPs reacted with M2 to form imine bonds. In addition, M3, which had twice the number of aldehyde groups as M2, enabled SPs to ring-close, causing the proceeding of crosslinking process at the same time. Thus linear SPs were transformed into poly[2]catenane gel networks. Due to the presence of hydrogen bonds in the poly[2]catenane gel, the gel also possessed stimulus responsiveness and self-healing properties.

Cu-catalyzed electrochemical CO ₂ reduction reaction (CO ₂RR) and CO reduction reaction (CORR) are of great interest due to their potential to produce carbon-neutral and value-added multicarbon (C ₂₊) chemicals. In practice, CO ₂RR and CORR are typically operated at industrially relevant current densities, making the process exothermal. Although the increased operation temperature is known to affect the performance of CO ₂RR and CORR, the relationship between temperatures and kinetic parameters was not clearly elaborated, particularly in zero-gap reactors. In this study, we detail the effect of the temperature on Cu-catalyzed CO ₂RR and CORR. Our electrochemical and operando spectroscopic studies show that high temperatures increase the activity of CO ₂RR to CO and CORR to C ₂H ₄ by enhancing the mass transfer of CO ₂ and CO. As the rates of these two processes are highly influenced by reactant diffusion, elevating the operating temperature results in high local CO ₂ and CO availability to accelerate product formation. Consequently, the *CO coverage in both cases increases at higher temperatures. However, under CO ₂RR conditions, *CO desorption is more favorable than carbon-carbon (C—C) coupling thermodynamically at high temperatures, causing the reduction in the Faradaic efficiency (FE) of C ₂H ₄. In CORR, the high-temperature-augmented CO diffusion overcomes the unfavorable adsorption thermodynamics, increasing the probability of C—C coupling.

A novel method for synthesizing α-oxygen organoboron compounds has been developed through acylsilane-based carbene insertion reactions into C—B bonds. As coupling partners, readily available organoboron compounds (alkenyl, allyl, and allenyl B(pin)) were employed. Based on the substrates, pure insertion into C—B bonds or insertion followed by a siloxy group rearrangement process (from carbon to boron) would occur, delivering the α-oxygen organoboron compounds with great diversities. Control experiments demonstrated that the electronic effect of the substituents mainly controlled the rearrangement process. Besides, no matter which isomer of substrate ( Z or E) was used, the reaction with β-aryl-substituted alkenyl B(pin) affords both isomers of products ( Z and E, separable through column chromatography). Trapping experiments indicated the triplet energy transfer process was involved.

Kagome lattices have garnered significant attention due to their promising applications in catalysis, electronics, and magnetics. Although many efforts have been paid to the design and synthesis of Kagome lattices, there is a limited focus on constructing this lattice by multiple interaction forces. In this work, we employ 2, 7-dibromo-carbazole as precursors to successfully fabricate the two-dimensional self-assembly Kagome lattices stabled by multiple interaction forces on Au(111) substrate. Using low-temperature scanning tunneling microscopy, non-contact atomic force microscopy and density functional theory calculation, we visualize and identify the four interaction forces within Kagome lattices: Au—N coordination bonds, Au—H hydrogen bonds, Br—Br halogen bonds, and Br—H hydrogen bonds, respectively. This study provides a basic understanding for designing and constructing more complex Kagome lattices.

Discovery of unprecedented donor-acceptor patterns can essentially enrich the chemistry of donor-acceptor cyclopropanes. We herein introduce a concept of vinylogous fluorine stabilizing effect, which guides rational design of a novel donor-acceptor cyclopropane employing gem-difluorovinyl group as the electron donor, namely dFVCP. Application of such dFVCPs in a [3+2] cycloaddition with aldehydes and a controlled ring-opening polymerization by a Mg(OTf) ₂/DIPEA/C(sp ³)-H initiator system have been demonstrated, providing direct access to fluorine-containing tetrahydrofurans and all-carbon main-chain polymers.

TAG-assisted peptide synthesis technology enables optimal conservation of Fmoc amino acid raw materials and chemical solvents while eliminating the need for intricate chromatographic purification processes. This work presents a 4, 4’-diphenylphosphonoxy diphenylcarbinol tag-mediated liquid-phase synthesis approach for preparing side-to-tail cyclopeptides macolacin which has strong activity against gram-negative bacteria, and its 15 analogues containing four N-methylation modified cyclopeptides, as well as an investigation of their structure-activity relationship (SAR). The synthesis of macolacin analogues primarily focuses on the modifications of the N-methylation group of Ile-7 and the tail fatty acyl chain of macolacin. The incorporation of N-methylation for Ile-7, along with the dihalogenated or monohalogenated benzoic acids for tail modification, exhibited remarkable antibacterial efficacy and minimal hepatocellular toxicity in vitro. The present study identified an N-methylation-modified antimicrobial cyclopeptide Ma14 that exhibits rapid bactericidal efficacy against A. baumanii, etc., while showing reduced hepatocellular toxicity. Molecular docking simulations were conducted to investigate the binding of cyclopeptides to the outer membrane protein BamA of A. baumannii. The findings demonstrated the stable binding interactions of the cyclopeptides with the BamA protein and then presented a novel approach to explain the bacteriostatic mechanism of macolacin-based cyclopeptide antibiotics.

A novel electrocatalyst, Ni-Co/β-Mo ₂C@C, was rationally designed to enhance the efficiency of the hydrogen evolution reaction (HER) in this work. Assembled with two-dimensional Ni-Co nanosheets onto Mo ₂C nanorods coated with a thin carbon shell, the catalyst demonstrates remarkable performance, including low overpotential ( η ₁₀ = 57 mV) and reduced Tafel slope (63 mV·dec ^-1) in 0.5 mol·L ^-1 H ₂SO ₄ electrolyte. This innovative design strategy provides abundant active sites and efficient electron/ion transport pathways, effectively shortening reactant diffusion distances and enhancing electrocatalytic activity. Additionally, the carbon shell coating protects the catalyst from etching and agglomeration, ensuring its durability. This work presents a promising approach for engineering highly efficient metal carbide-based HER catalysts through tailored composition and nanostructure design.

Comprehensive Summary: The EDA complex-mediated reactions involving oxime esters have been few studied. Herein, an EDA complex formed by thiophenolate anion and oxime ester is reported for photoinduced divergent synthesis of thioethers, depending on different types of oxime esters. Operational simplicity, mild reaction conditions, and flexible options of leaving group demonstrate the generality and synthetic utility of this approach. Such an approach can also enable an interesting thiol-catalysis for the synthesis of phenanthridines.

Designing new materials and architectures to maintain activity and stability requires a better understanding on the anticorrosion dynamics of nanoparticles. Under-coordinated atoms on the surface of nanoparticles can be protected by deposited shells. Real-time observation on how protective shells grow and play a role is challenging but worthwhile. Here, protective effects of AuCl ₃ shells on Au nanobipyramids (NBPs) are studied in HAuCl ₄ aqueous solutions by in-situ liquid cell transmission electron microscopy (LCTEM). This study is the first to observe the formation of Au-AuCl ₃ core-shell nanostructure and the corresponding anticorrosion behaviors of AuCl ₃ deposited shell. The presence of CTAB can substantially influence the growth mode and structure of AuCl ₃ shell, by a direct or indirect way, intervene the dissolution of Au NBP. These growth or dissolution kinetics here revealed at the nanoscale provide insights towards engineering of the surface anticorrosion to pursue Au nanoparticles with improved stability in acidic environment.

Carbonylation reactions are a valuable synthetic method to construct carbonyl compounds and carbonylation reactions of aryl halides stand out as a highly significant tool for generating carbonyl substituted arenes. However, the important reactions have never been realized in aromatic metallacycles. Herein, we present the first carbonylation reactions of metallaaromatics, specifically alkoxycarbonylation and aminocarbonylation reactions of an osmapentalyne. During the carbonylation process, the electronic and steric properties of nucleophiles are regarded as critical factors. The alcohols with bulky substituents (isopropanol) require more reaction time and tert-butyl alcohol is inert in the reaction. Comparatively, amines, being stronger nucleophiles, exhibit divergent behaviors. Bulky amines undergo aminocarbonylation, whereas small amines prefer direct nucleophilic additions. Control experiments revealed that the intermediate derived from coupling of metal carbyne with CO plays a significant role in the carbonylation reaction. According to these observations, a divergent pathway for the reaction is proposed. Furthermore, the photophysical properties of these carbonyl-functionalized osmapentalene complexes are studied, and the maximum absorption peak of compound with a carboxylic group exhibits a significant red-shift due to the smaller HOMO-LUMO gap. These findings contribute to expanding the reactivity of metallaaromatics and offer new opportunities for the synthesis of carbonyl-functionalized metallacycles.

A regiodivergent synthesis of azetidines, 5, 6-dihydro-1, 3-oxazines and 2, 3-dihydro-1, 4-oxazines has been achieved through palladium-catalyzed tandem allylic substitution reaction. This protocol provides a variety of heterocycles in satisfactory yields with good to excellent regioselectivities under mild reaction conditions.

Inorganic lead halide perovskite (LHP) nanostructures, represented by formula CsPbX ₃ (X = Cl, Br, I), have garnered considerable interest for their exceptional optical properties and diverse applications. Despite their potential, challenges such as environmental degradation persist. In-situ synthesis within protective materials pores is a promising way to address this issue. However, confining perovskite nanostructures into porous matrices during the synthesis can limit their photoluminescence quantum yield (PL QY) and tunability of optical properties. Various post-treatment approaches exist to improve the properties of LHP and achieve their desired functionalities, but these strategies have not been explored for LHP confined in mesoporous matrices. Here, we demonstrate the efficacy of in-situ post-synthetic treatments to improve the optical properties of CsPbBr ₃ nanocrystals grown in nanoporous silica microspheres. Surface passivation with Br ^– ion-containing precursors boosts PL QY, while anion-assisted cation doping with Mn ²⁺ ions introduces a new PL band. The adjustment of precursor amount and doping duration enables precise control over the optical properties of LHP, while additional coating with a SiO ₂ shell enhances their stability in polar solvents, expanding the potential applications of these composites.

Electrocatalytic reduction of CO ₂ to valuable products possesses huge potential to alleviate environmental and energy crisis. It is well known that Ag favors the conversion of CO ₂ to CO but the exposed active sites and stability are still rather limited. In this study, a novel one-dimensional Ag-based metal-organic framework (1D Ag-NIM-MOF) was successfully synthesized and used in the electrocatalytic CO ₂ reduction reaction (CO ₂RR) for the first time. As a result, the Faradaic efficiency of CO achieved 94.5% with current density of 12.5 mA·cm ^-2 in an H-type cell and 98.2% with current density of 161 mA·cm ^-2 in a flow cell at -1.0 V (vs. RHE), which stands as a new benchmark of Ag-based MOFs in the electrocatalytic CO ₂RR. The excellent performance of 1D Ag-NIM-MOF is attributed to its peculiar one-dimensional structure, which is beneficial for diffusion of reactants and products, and exposure of much more catalytic sites. Compared to commercial Ag nanoparticles, 1D Ag-NIM-MOF exhibits superior electrocatalytic CO ₂RR performance with higher catalytic activity and stability.

Inverted (p-i-n) perovskite solar cells (PSCs) are favored by researchers owing to their superior compatibility with flexible substrates and tandem device fabrication. Additionally, the hole transport layer (HTL) serves as a template for perovskite growth, which is critical for enhancing the device performance. However, the current research on how the HTL promotes perovskite crystallization is insufficient. Here, 4PADCB, a self-assembled monolayer (SAM) hole transport material, was optimized as a superior template for perovskite growth through comparative analysis; accordingly, compact perovskite film with vertical growth was prepared. The better matched energy level alignment between 4PADCB and perovskite suppressed nonradiative recombination at the interface and enabled rapid hole extraction. Moreover, high-quality perovskite film growth on 4PADCB exhibited lower Young’s modulus and less residual stress. By integrating 4PADCB into p-i-n PSCs, the optimal device achieved a power conversion efficiency of 24.80%, with an open-circuit voltage of 1.156 V, thus achieving the best rank among devices without perovskite post-treatment, additives, dopants, or intermediate layers. Furthermore, the unencapsulated device demonstrated exceptional thermostability and photostability under maximum power point tracking. Thus, this work provides a new understanding for the development of novel SAMs and perovskite growth, and it is expected to further improve device performance.

A greener and more convenient alternative to traditional methods for the generation of thiyl radical as hydrogen atom transfer (HAT) catalyst is developed, using molecular oxygen to oxidize thiol without the need for chemical initiators or light irradiation. The thiol/oxygen catalysis enables selective and efficient difunctionalization of borane.

Carbohelicenes have garnered considerable attention for their inherent chirality and structural flexibility. Increasing multi-helicity and incorporating non-six-membered rings to substitute benzenoid rings within helicenes are effective strategies for introducing unique photoelectric properties. Despite the disclosure of numerous helicenes, the inaccessible precursors and the lack of synthetic routes pose a challenge in achieving desired helicene structures fused with non-benzenoid rings. Herein, we report the synthesis of multiple non-benzenoid carbohelicenes fused with fluorene unit(s) through intramolecular cyclodehydrogenation of 9, 10-di(naphthalen-1- yl)anthracene on Au(111) surface. Two potential cyclodehydrogenation manners between naphthyl and anthracene lead to the formation of fluorene-fused [5]helicene and [4]helicene moiety. Consequently, a total of four stable products were observed. The atomic topographies of products are characterized by bond-resolving scanning tunneling microscopy. The chiral helicity of targeted products can be switched by tip manipulation. Density-functional-theory calculations unveils the reaction pathway of four products. The comparative analysis of their respective energy barriers exhibits a correlation with the experimentally determined yields. Furthermore, we synthesize the polymer chains incorporating non-benzenoid carbohelicenes via the Ullmann reaction of 2, 6-dibromo-9, 10-di(1-naphthyl)anthracene precursors. Our work proposes a synthetic methodology for several novel helicene-like structures fused with fluorene units and the polymer bearing helicene subunits, thus highlighting the immense potential of these compounds in the application fields of luminescent electronic devices.

Catalytic dehydrogenation, with its exceptional atom economy and chemoselectivity, offers a highly desirable yet challenging approach for converting multiple environmentally friendly alcohols into crucial molecules. Furthermore, the utilization of catalysts based on abundant elements found on Earth for alcohol dehydrogenation to produce acryl ketone holds significant promise as a versatile strategy in synthesizing key building blocks for numerous pharmaceutical applications. The present study describes a practical Co-catalyzed cascade dehydrogenative Claisen condensation of secondary alcohols with esters, facilitating the synthesis of a wide range of 3-hydroxy-prop-2-en-1-ones. We introduce a catalytic system based on novel and scalable indazole NNP-ligands coordinated to cobalt for efficient dehydrogenations of secondary alcohols, and propose a plausible reaction mechanism supported by control experiments and labeling studies. Notably, it allows for the streamlined synthesis of multiple pharmaceuticals in one-pot.

The morphology of the active layer plays a crucial role in the performance of organic photovoltaics. Although volatile additives are commonly used to manipulate the morphology, their mechanism of action remains poorly understood. In this study, we conducted a systematic exploration of the mechanism of the traditional volatile additive 1-CN in film formation kinetics of typical PM6:Y6 system. We found that 1-CN induces a secondary aggregation effect, improving film morphology and promoting face-on crystalline orientation. Through elucidating its impact on exciton dynamics, we established a link between morphology optimization and increased exciton diffusion length and accelerated charge separation. Our findings unveil the unique mechanism of action of volatile additive, providing a new perspective for improving the morphology and enhancing the performance of organic photovoltaic devices.

The first catalytic asymmetric total synthesis of (+)-propolisbenzofuran B, enabled by a highly enantioselective rhodium-catalyzed hydrogenation of a tetrasubstituted olefin, was described. Other noteworthy aspects include the construction of the central hydrodibenzo[ b, d]furan core through a sequence of Zn(II)-mediated regioselective benzofuran formation and Dieckmann condensation, as well as C-H oxidations, involving a visible light-induced Fe(III)-catalyzed benzylic C(sp ³)-H oxidation. Additionally, the absolute configuration was confirmed by X-ray analysis of a carbonate intermediate.

Poly-NHC-based organometallic assemblies 3-PF ₆, 3-SbF ₆ and 3-OTf were obtained and verified by NMR spectroscopy, ESI mass spectrometry and single-crystal X-ray diffraction analyses. Controllable structural interconversion was observed between the poly-NHC-based organometallic assemblies and their self-aggregated dimers in solution affected by concentration, solvent and metal ion. ¹H NMR spectra of assembly 3-PF ₆ in CD ₃CN at different concentrations demonstrated controllable structural interconversion, and ¹⁹F NMR spectrum of assembly 3-PF ₆ at high concentration further evidenced the presence of the free hexafluorophosphate anion and encapsulated hexafluorophosphate anion for its two sets of signals. In addition, single-crystal X-ray diffraction analysis provided clear evidence that in the solid state, two assemblies 3-PF ₆ were vertically stuck, forming a self-aggregated dimer with an encapsulated hexafluorophosphate anion. Investigating the reversible structural interconversion is beneficial for revealing the intrinsic nature on the atom level and paving the way to design the stimuli-responsive functional system.

Development of heterogeneous molecular photocatalysts for promising light-driven hydrogen evolution reaction (HER) is highly demanding but still challenging. Here, we report the blue-greenish emitting dinuclear metal–organic halides as photocatalyst by incorporating site-specific single copper(I) atoms that exhibit an efficient carbon-negative H ₂ production. Interestingly, the electronic properties, including the spin and charge density of central Cu(I) active site, can be triggered by substituent modulation in metal–organic halides, which greatly affect the exciton dissociation kinetics and thus the HER reactivity. The optimized spin density in these heterogeneous photocatalysts drastically boosts the hydrogen production rate from 1250 to 3130 µmol·g ^-1·h ^-1. Our molecular strategy provides a platform that rationally facilitates electronic modulation of copper(I) atoms, tunes the macroscopic optoelectronic properties of photocatalysts and boosts carbon-negative HER activity, extending the boundaries of conventional molecular-based photocatalysts.

Comprehensive Summary: Amorphous nanomaterials are metastable nanomaterials which only have short-range order within a few neighboring atoms, based on the local chemical bondings. Different from crystalline materials, the amorphous nanomaterials lack of long-range order exhibit many intriguing and unique structu ral features, such as abundant active sites, structural flexibility, intrinsic isotropy and fast ionic transport. However, due to the unco nventional structural complexity, the systematic study and understanding of amorphous nanomaterials are still in the early stage. In this review, we will describe our journey to the synthesis, characterization and applications of amorphous nanomaterials, including catalysis, energy storage, optics and mechanics.

What is the most favorite and original chemistry developed in your research group?

Our group developed a variety of universal methods, such as “coordination etching” method, “self-hydrolytic etch-precipitation” method, photoetching method, co-precipitation method,etc., to achieve the controllable preparation of amorphous nanomaterials with different morphology, size and dimension, and the catalytic, mechanical and optical properties of the materials and their potential applications were also studied. Moreover, the relevant mechanisms were proposed, the structure-activity relationship was established, and the development and application of amorphous micro-nanomaterials were promoted.

How do you get into this specific field? Could you please share some experiences with our readers?

My journey into the field of amorphous nanomaterials began 20 years ago when I developed a fascination for materials science and nanotechnology. During my early research experiences, I encountered the intriguing world of amorphous nanomaterials. These materials, lacking a long-range crystalline order, presented both challenges and opportunities in terms of their synthesis and understanding their properties. It’s a field where creativity and precision intersect, driving me to continually seek innovative solutions and deepen my understanding of nanoscale phenomena.

How do you supervise your students?

As a professor, I supervise students by setting clear expectations, holding regular meetings for feedback and guidance, and encouraging

independent thinking. I support their career development by identifying opportunities and creating a collaborative environment. Adapting to individual needs, I foster a fair and consistent approach to help students grow professionally and academically.

What is the most important personality for scientific research?

One of the most important traits for scientific research is curiosity. It drives researchers to ask questions, explore new ideas, and seek innovative solutions. Curiosity fuels the desire to understand the unknown, propelling scientific discovery and breakthroughs. Additionally, persistence is crucial as research often involves challenges and setbacks that require perseverance to overcome. Clear communication skills are also vital for sharing findings and collaborating effectively within the scientific community.

Who influences you mostly in your life?

As a researcher, my greatest influences come from my mentors, Prof. Hesun Zhu, Qianshu Li and Shihe Yang who guide my academic journey and collaborators who inspire new ideas and perspectives. My mentors, who provide guidance and expertise play a crucial role in shaping my approach to research and career development. Their insights and support empower me to navigate challenges and continuously strive for excellence in my scientific endeavors.

What are your hobbies?

My hobbies are a blend of activities that complement and enrich my professional life. I enjoy participating in discussions and workshops within my academic community, where I can exchange ideas and learn from peers outside of formal research settings.

Comprehensive Summary: Graphene nanoribbons (GNRs), which can be considered as a special type of conjugated polymers, are quasi-one-dimensional graphene cutouts with an opened band gap, revealing great potential as functional materials in optoelectronic, spintronic, and energy-related applications. An effective strategy to modulate the properties of GNRs is doping heteroatoms into the π-skeleton. Thanks to the bottom-up synthetic approach, a number of heteroatom-doped GNRs with precise structures have been reported, exhibiting intriguing properties. Nevertheless, a comprehensive summary of the progress of this field has remained elusive. In this review, we summarize the history and advances in bottom-up synthesized heteroatom-doped GNRs, including their synthetic routes, electronic properties, and promising applications. We hope to establish the reliable structure–property relationship, and provide guidance for the molecular design of heteroatom-doped GNRs in the future.

With rational designability, versatile tunability, and quantum coherence, molecular electron spin qubits could offer new opportunities for quantum information science, enabling simplified implementation of quantum algorithms and chemical-specific quantum sensing. The development of these transformative technologies relies on coherent addressing of single molecular electron spin qubits with high initialization, manipulation, and readout fidelities. This is unfeasible to conventional electron spin resonance spectroscopy, which is widely used for coherent addressing of ensemble electron spins, due to its low initialization efficiency and readout sensitivity. Taking advantage of single spin detectability of single-molecule spectroscopy, scanning tunneling microscopy, atomic force microscopy, and quantum metrology, several strategies have been developed to empower electron spin resonance spectroscopy with single qubit addressability. In this Emerging Topic, we introduce principles and technical implementation of strategies for coherent addressing of single molecular electron spin qubits, discuss their potential applicability in quantum technologies, and point out their challenges in terms of scalability, molecular design, and/or decoherence suppression. We discuss future directions to overcome these challenges and to improve single qubit addressing technologies, which will facilitate the advancement of molecular quantum information science.

Comprehensive Summary: Advanced functionalization-decorated porous organic polymers (POPs) are emerging as a prominent research focus, spanning from their construction to applications in gas storage and separation, catalysis, energy storage, electrochemistry, and other areas. Furthermore, the inherent organic nature, tailored pore structures, and adjustable chemical components of POPs offer a versatile platform for the incorporation of various metal active sites. Meticulously designed molecular building blocks can serve as organic ligands uniformly distributed throughout POPs, leading to the effective isolation of inorganic metal active sites at the molecular level. In this manner, POPs containing active metal centers bridge the gap between organic and inorganic scaffolds. This review aims to provide an overview of recent research progress on metal-decorated POPs, focusing on strategies for incorporating metal active sites into POPs and their applications in adsorption, separation, catalysis, and photoelectrochemistry. Finally, current challenges and future prospects are discussed for further research.

Key Scientists: Advanced functionalized porous organic polymers have become a new research hotspot, ranging from their construction to their use in gas storage and separation, catalysis, energy storage, electrochemistry, and other applications. In 2002, the McKeown group was the first to report phthalocyanine-based MPOPs with permanent porosity and a moderate surface area. In 2010, the Yu group prepared nanoporous polyporphyrin materials P(Fe-TTPP) from the metallated porphyrin with functionalized thiophenyl groups by the FeCl₃ catalyzed oxidation couple reaction showing the surface area of 1522 m²·g^-1. Subsequently, in 2013, the Deng group was the first to use metalated salens as the original building blocks for preparing MPOPs. The Morin group was the first to produce a series of ferrocene-based nanoporous frameworks via radical polymerization, with surface areas ranging from 385 to 899 m²·g^-1. In 2016, the Han group synthesized two N-pyridinylphenylcarbazole (PPC) ligands to produce a series of metalized polycarbazole networks. Recently, the Tan group reported a solvent-knitting hyper-cross-linking reaction to produce HUST-1, which contains a porphyrin unit. The porphyrin moiety provides a centered square-planar metal post-coordination site, resulting in the metalated HUST-1-Co, which exhibits high efficiency in the catalytic conversion of CO₂. Additionally, the Kegnæs group combined the decomposition of the palladium complex with an in situ catalyzed polymerization reaction, enabling the confinement of nascent Pd particles in the developing polymer network. This review focuses on recent research progress in metal-decorated POPs, emphasizing strategies for incorporating metal active sites into POPs and their applications.