Chinese Journal of Chemistry最新文献

{"title":"π-Conjugated Surface Modification and Supramolecular Assembly of a Homochiral Zirconium-Embonate Cage for Tunable Optical Properties","authors":"Yan-Ping He,&nbsp;Xiao-Lan Zheng,&nbsp;Xin Meng,&nbsp;Dong-Xin Guan,&nbsp;Si-Le Luo,&nbsp;Bao Liu,&nbsp;Jinyan Zhang,&nbsp;Ping Lan,&nbsp;Yan-Xi Tan,&nbsp;Qiao-Hong Li,&nbsp;Jian Zhang","doi":"10.1002/cjoc.70653","DOIUrl":"https://doi.org/10.1002/cjoc.70653","url":null,"abstract":"<div>\u0000 \u0000 <p>The unique combination of solution processability, modular synthesis, and post-synthetic modification (PSM) capabilities renders metal–organic cages (MOCs) a highly promising platform for diverse applications. In this work, a pair of pure enantiomers, <b>PTC-377(Λ,S)</b> and <b>PTC-377(Δ,R)</b>, were synthesized via selective coordination of π-conjugated chiral cations, [Ag₂(1<i>S</i>,2<i>S</i>-DPEN)(DPPM)]²⁺ and [Ag₂(1<i>R</i>,2<i>R</i>-DPEN)(DPPM)]²⁺, to the vertices of racemic ΔΔΔΔ- and ΛΛΛΛ-Zr₄L₆ (L = embonate) cage precursors, respectively. The chiral resolution and surface modification of the zirconium cage result in a pronounced circularly polarized luminescence (CPL) response. Furthermore, the loading of π-conjugated 1,10-phenanthroline (phen) within the mesoporous channels of <b>PTC-377</b> yields the composite <b>phen@PTC-377</b>. Thin films of this composite exhibit a dramatically enhanced optical limiting effect, with the normalized transmittance minimized at 0.11—a significant improvement over both the pristine Zr₄L₆ cage (~1) and the parent <b>PTC-377</b> (~0.65). According to theoretical calculations, the enhanced optical limiting effect originates from the strong π–π stacking at the edge site between phen and the <b>PTC-377</b> framework, these interactions extend the conjugated system and facilitate efficient charge transfer, thereby enhancing the polarizability and hyperpolarizability of the molecule.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 16","pages":"2735-2742"},"PeriodicalIF":5.7,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148532501","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Energy Transfer Catalysis Enabled Fluoro-sulfonylation/-sulfonimidation with Fluoride†","authors":"Juanjuan Wang,&nbsp;Huilin Zhan,&nbsp;Qiang Cheng","doi":"10.1002/cjoc.70658","DOIUrl":"https://doi.org/10.1002/cjoc.70658","url":null,"abstract":"<div>\u0000 \u0000 <p>Sulfonyl and sulfonimidoyl fluorides serve as versatile SuFEx hubs for forming diverse bonds at the S(VI) center, with applications in medicinal chemistry, chemical biology, and materials science. Their state-of-the-art synthesis via modular fluorosulfonylation and fluorosulfonimidation typically relies on the use of acidic fluoride salts and suffers from slow reaction kinetics, primarily due to the intermediacy of the widely adopted S(VI)-DABCO adducts generated through redox processes. On the other hand, aryl thiophenium salts have been recognized in energy transfer catalysis for their ability to generate aryl radicals and thiophenium radical cations, a reactivity profile that has been exploited in radical coupling with ethylene. Despite this promise, their application in other radical-radical coupling manifolds remains underexplored. Herein, we report a highly efficient radical-radical cross-coupling strategy for assembled fluorosulfonylation and fluorosulfonimidation with aryl thianthrenium salts using cesium fluoride under energy transfer catalysis. The substantial advances stem from the energy transfer process that generates the persistent thianthrenium radical cation and subsequently results in formation of the key highly electrophilic S(VI)-thianthrenium species, which have enabled fast reaction kinetics with broad functional group tolerance. Mechanistic studies provided compelling evidence for the proposed pathway: the aryl radical was intercepted by TEMPO and BHT, while the pivotal S(VI)–thianthrenium intermediate was directly detected by high-resolution mass spectrometry. The reaction can be easily scaled up and readily applied for late-stage functionalization. To be noted, our strategy allows, for the first time, highly regioselective fluorosulfonimidation of aromatics with fluoride. The exceptional regiochemical outcome is attributed to the inherent site selectivity of the thianthrenation step, combined with the superior reaction kinetics imparted by the highly reactive S(VI)-thianthrenium intermediates. Both the resulting sulfonyl fluorides and sulfonimidoyl fluorides undergo SuFEx reactions smoothly under mild conditions, providing rapid access to complex molecules with diverse S(VI)-functional groups.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 16","pages":"2727-2734"},"PeriodicalIF":5.7,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148522843","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photoredox/Copper Dual-Catalyzed Formal α-Nucleophilic Addition to α,β-Unsaturated Enones for the Synthesis of Chiral γ-Lactones","authors":"Pengfei Zhou,&nbsp;Ziyu Jin,&nbsp;Qiuping Ding,&nbsp;Yahan Zhang,&nbsp;Jian-Qiang Chen,&nbsp;Jie Wu","doi":"10.1002/cjoc.70654","DOIUrl":"https://doi.org/10.1002/cjoc.70654","url":null,"abstract":"<div>\u0000 \u0000 <p>The inherent polarity mismatch suggests that direct α-nucleophilic addition is disfavored both thermodynamically and kinetically under conventional conditions. However, indirect α-nucleophilic addition reactions of α,β-unsaturated carbonyl compounds via copper-catalyzed radical pathways have been well established. Herein, we reported a formal asymmetric α-nucleophilic addition reaction of α,β-unsaturated carbonyl compounds through merging photoredox catalysis with copper catalysis. This transformation proceeds via radical addition to an α,β-unsaturated carbonyl compound, followed by a C–O bond cross-coupling reaction to afford the corresponding chiral γ-lactones. With this strategy, a diverse range of chiral γ-lactones bearing a quaternary stereocenter could be afforded.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 16","pages":"2719-2726"},"PeriodicalIF":5.7,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148532502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multi-Pathway Photochemical/Manganese-Catalyzed Diazidation of Alkenes","authors":"Mengdi Chen,&nbsp;Chen-Xi Xia,&nbsp;Xin-Lei Sun,&nbsp;Yue Ren,&nbsp;Jinfeng Zhang,&nbsp;Kuai Wang,&nbsp;Ling-Guo Meng","doi":"10.1002/cjoc.70665","DOIUrl":"https://doi.org/10.1002/cjoc.70665","url":null,"abstract":"<div>\u0000 \u0000 <p>Vicinal diamines, recognized for their attractive structural motifs and functional versatility, are widely used in pharmaceuticals, catalysis and functional materials. As the best choice, the diazidation of alkenes offers an efficient route for the rapid decoration of diazide compounds, which can be converted to the corresponding diamines via a simple reduction step. Although advanced strategies for alkene diazidation, primarily involving radical ligand transfer or a combination of radical ligand transfer and ligand-to-metal charge transfer, have been developed, most of the methods still face some limitations, such as the requirement for superstoichiometric oxidants, and notably differ substantially in substrate applicability. To address this shortcoming, we combine IBA-N₃ with <i>in-situ</i> generated Mn^II-N₃ to establish a synthetic strategy that can cover most of the different known pathways to incorporate the azide group into diazide compounds. Consequently, this protocol can significantly increase the suitable range of alkenes by overlapping multiple pathways to obtain azide sources. Mechanistic analysis indicates that this transformation strategy can include redox, photochemical homolysis of I^III-N₃, radical ligand transfer and radical group transfer processes to form a practical design to achieve alkene diazidation with a better scope of alkene tolerance.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 16","pages":"2779-2784"},"PeriodicalIF":5.7,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148533093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stabilizing Ruthenium(I) Radicals with N-Heterocyclic Carbene and Arene Ligands","authors":"Qi Chen,&nbsp;Xuebing Leng,&nbsp;Dongyang Wang,&nbsp;Liang Deng","doi":"10.1002/cjoc.70648","DOIUrl":"https://doi.org/10.1002/cjoc.70648","url":null,"abstract":"<div>\u0000 \u0000 <p>Ru(I) radicals with a 4<i>d</i>⁷ electronic configuration are sought after for their unique electronic structure and synthetic utility in chemical transformations. However, due to their high reactivity, ligand scaffolds effecting the stabilization of Ru(I) species are exceedingly rare. In this study, we present readily accessible, persistent Ru(I) radicals supported by <i>N</i>-heterocyclic carbenes (NHCs) and <i>p</i>-cymene, [RuCl(NHC)(<i>η</i>⁶-<i>p</i>-cymene)]. These halide complexes are easily prepared <i>via</i> single-electron reduction of their Ru(II) dichloride precursors. Integrated single-crystal X-ray diffraction, EPR spectroscopy, magnetic measurements, and DFT studies establish an <i>S</i> = 1/2 ground state with spin density primarily localized on ruthenium. Frontier molecular orbital analysis indicates that the stabilization of these Ru(I) radicals originates from the synergistic interplay of the strong σ-donation from the NHC ligand and δ-acceptance of the arene ligand. Accordingly, voltammetry study showes a reversible one-electron oxidation at relatively high potential (<i>E</i>_1/2 = –0.32 V vs. <i>SCE</i>) and an irreversible one-electron reduction at very low potential (<i>E</i>_p = –2.17 V vs. <i>SCE</i>). Furthermore, the chloride ligand in these Ru(I) complexes allows chloride-to-phosphine exchange reaction as demonstrated by the preparation of the cationic Ru(I) complex [Ru(PMe₃)(IMes)(<i>η</i>⁶-<i>p</i>-cymene)][BPh₄] from the reaction of [RuCl(IMes)(<i>η</i>⁶-<i>p</i>-cymene)] with PMe₃ and NaBPh₄, underscoring their utility as tunable precursors for catalysis.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 16","pages":"2765-2771"},"PeriodicalIF":5.7,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148533466","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pd/Xu-Phos-Catalyzed Synthesis of Alkenyl Allenes via β-H Elimination of 1,3-Dien-1-yl Triflates","authors":"Haichao Shen,&nbsp;Jie Han,&nbsp;Kunhua Li,&nbsp;Junfeng Yang,&nbsp;Junliang Zhang","doi":"10.1002/cjoc.70652","DOIUrl":"https://doi.org/10.1002/cjoc.70652","url":null,"abstract":"<div>\u0000 \u0000 <p>Alkenyl allenes represent a privileged subclass of allenes; the conjugation between the cumulated diene and the adjacent alkenyl group imparts distinctive chemical behaviors, rendering them valuable precursors for complex molecular architectures via transformations such as Diels–Alder cycloadditions and Nazarov cyclizations. Palladium-catalyzed β-hydride (β-H) elimination represents a fundamental and well-established strategy in organic synthesis, extensively utilized for the preparation of allenoates and aryl allenes. However, extending this powerful transformation to the synthesis of conjugated alkenyl allenes has historically proven to be a formidable challenge. This synthetic difficulty arises primarily from the intrinsic thermodynamic instability of the alkenyl allene motif, which is notoriously prone to rapid isomerization into more stable conjugated polyenes, often resulting in complex mixtures of byproducts and preventing the isolation of the desired compound. To address this long-standing limitation and achieve high selectivity, we herein report a robust and highly efficient protocol for the selective synthesis of alkenyl allenes via the Pd/Xu-Phos-catalyzed β-H elimination of 1,3-dien-1-yl triflates. Central to the success of this method is the identification and application of the sterically tuned Xu-Phos ligand. This bulky, electron-rich phosphine ligand effectively facilitates the challenging elimination step, while simultaneously suppressing the competitive hydropalladation and subsequent isomerization pathways that have plagued previous attempts. The reaction is proposed to proceed through an acetate-assisted intramolecular deprotonation manifold. Consequently, this methodology features exceptionally mild reaction conditions and demonstrates broad functional group compatibility. It provides general access to diverse di- and trisubstituted alkenyl allenes in high yields and excellent selectivities. These products serve as pivotal precursors for the construction of complex bicyclic scaffolds via subsequent cyclization reactions, thereby opening new avenues for the synthesis of bioactive natural products and pharmaceuticals.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 16","pages":"2759-2764"},"PeriodicalIF":5.7,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148533556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fully Non-Fused Organic Photovoltaic Systems Based on a Pyrazine-Functionalized Polymer Donor","authors":"Enhui Zhai,&nbsp;Huixue Li,&nbsp;Junzhen Ren,&nbsp;Jiangbo Dai,&nbsp;Zhihao Chen,&nbsp;Jianqiu Wang,&nbsp;Shuohan Cheng,&nbsp;Wenye Xu,&nbsp;Shaoqing Zhang","doi":"10.1002/cjoc.70651","DOIUrl":"https://doi.org/10.1002/cjoc.70651","url":null,"abstract":"<div>\u0000 \u0000 <p>Solution-processable organic photovoltaic (OPV) cells show promise for industrialization; however, high-performance polymer donors often rely on costly fused-ring structures. Here, we propose a novel polymer donor, 4T-Pz, which is a low-cost, fully non-fused donor featuring a pyrazine-based structure. Benefiting from the energy-level modulation induced by pyrazine units and enhanced backbone planarity, 4T-Pz exhibits a deep HOMO level (–5.38 eV), pronounced solution-state pre-aggregation, and favorable molecular packing behavior, thereby facilitating efficient charge generation and transport. When blended with two non-fused acceptors, A4T-16 and TBT-26, to form fully non-fused active layers, the optimized OPV cells deliver power conversion efficiencies of 14.2% and 12.7%, respectively. The 4T-Pz:A4T-16 system shows superior performance due to lower energy loss, weaker trap-assisted recombination, a uniform fibrous film morphology, and compact face-on π–π stacking, which favors charge transport. Cost analysis confirms competitiveness of 4T-Pz, with materials-only cost (MOC) of 11.63 USD·g^–1, far lower than that of fused-ring analogs. This work demonstrates the promise of pyrazine-based fully non-fused polymer donor in balancing performance and cost, and provides a viable materials-design route toward scalable, high-efficiency OPVs.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 16","pages":"2710-2718"},"PeriodicalIF":5.7,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148522725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synergistic Engineering of Crystalline Organoantimony-Selenite Clusters Enabling Water-Developable, High-Sensitivity Nanopatterning","authors":"Mei-Hua Xiong,&nbsp;Xi Liang,&nbsp;Juan Wang,&nbsp;Er-Xia Chen,&nbsp;Jin-Xia Yang,&nbsp;Jian Zhang,&nbsp;Qipu Lin","doi":"10.1002/cjoc.70628","DOIUrl":"https://doi.org/10.1002/cjoc.70628","url":null,"abstract":"<div>\u0000 \u0000 <p>The development of photoresists that combine high-sensitivity with environmental benignity is essential for advancing next-generation nanofabrication technologies. Herein, we present a molecular engineering strategy wherein selenite ligands are employed to assemble a series of dinuclear phenylantimony(oxo)-selenite clusters (designated as <b>α</b>, <b>β</b>, <b>γ</b>) with precisely tunable phenyl group densities, ranging from four to eight per cluster. A synergistic sensitivity mechanism is elucidated: the high-atomic-number (<i>Z</i>) inorganic core, comprising Sb and Se, functions as an efficient energy absorption antenna, while the surrounding shell of labile Sb–C bonds gives a high density of reactive initiation sites. Among the series, cluster γ exhibits optimal lithographic performance, achieving complete solubility switching at 26 μC·cm^–2, while maintaining sub-nanometer film smoothness. Notably, all resists are fully developable in pure water, underscoring their compatibility with environmentally sustainable processing. This work establishes a synergistic core-shell design principle for the development of high-performance, eco-friendly photoresists.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 16","pages":"2682-2688"},"PeriodicalIF":5.7,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148532552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reversible Transformations of Topology and Partial Interpenetrations in Metal-Organic Frameworks Triggered by Solid-State Photo/Thermal Reactions","authors":"Zi-Teng Wu,&nbsp;Zi-Yue Liu,&nbsp;Shu-Fen Zhang,&nbsp;Chun-Yan Yang,&nbsp;Bin Xu,&nbsp;Qi Liu,&nbsp;Jian-Ping Lang","doi":"10.1002/cjoc.70655","DOIUrl":"https://doi.org/10.1002/cjoc.70655","url":null,"abstract":"<div>\u0000 \u0000 <p>Reversible control of topology and partial-interpenetration transformations in metal-organic frameworks (MOFs) is vital for customizing their functional properties, but this area has long been insufficiently explored. Herein, we report the reversible regulation of both topology and partial-interpenetration in photo/thermal-responsive MOFs, focusing on the two-interpenetrated [Zn(<b><i>L</i></b>_{<b><i>1</i></b>})(H₂O)]_<i>n</i> (<b><i>L</i></b>_{<b><i>1</i></b>} = biphenylethene-4,4'-dicarboxylic acid). Through solid-state [2+2] cycloaddition reactions, this MOF was transformed into partially interpenetrated [Zn(<b><i>L</i></b>_{<b><i>1</i></b>})_<i>x</i>(<b><i>L</i></b>_{<b><i>2</i></b>})_1–<i>x</i>(H₂O)]_<i>n</i> (<i>x</i> represents the molar ratios of organic linkers) and non-interpenetrated [Zn(<b><i>L</i></b>_{<b><i>2</i></b>})(H₂O)]_<i>n</i> with different topology (<b><i>L</i></b>_{<b><i>2</i></b>} = 4,4',4”,4”'-(cyclobutane-1,2,3,4-tetrayl)tetrabenzoic acid, a cyclobutane derivative of <b><i>L</i></b>_{<b><i>1</i></b>}), and thermal treatment triggered reverse ring-opening to recover the original structure. These transformations were verified and visualized using single-crystal X-ray diffraction, synchrotron infrared spectroscopy, and other techniques. By introducing a third organic linker <b><i>L</i></b>_{<b><i>3</i></b>} (azobenzene-4,4'-dicarboxylic acid), we synthesized multivariate MOFs (MTV-MOFs, [Zn(<b><i>L</i></b>_{<b><i>1</i></b>})_<i>x</i>(<b><i>L</i></b>_{<b><i>3</i></b>})_1–<i>x</i>(H₂O)]_<i>n</i>) and precisely tuned their structural transformations by adjusting the ratio of the two linkers. By leveraging the inherent photoactivity of these MOFs and the photoexcited electrons generated during these structural transformations, they can be used to detect reductive molecules such as glucose. Their photocurrent-based glucose detection exhibited a high sensitivity of up to 780 μA·M^–1·cm^–2. This work enriches the structural diversity of MOFs and enhances their potential applications in adsorption and molecular recognition.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 16","pages":"2743-2752"},"PeriodicalIF":5.7,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148532503","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Topology Interlocking Drives the Construction and Application of Crystalline Porous Materials","authors":"Xianhui Tang,&nbsp;Bang Hou,&nbsp;Lei Jia,&nbsp;Enping Du,&nbsp;Yan Liu,&nbsp;Yong Cui","doi":"10.1002/cjoc.70668","DOIUrl":"https://doi.org/10.1002/cjoc.70668","url":null,"abstract":"<div>\u0000 \u0000 <section>\u0000 \u0000 <h3> Comprehensive Summary</h3>\u0000 \u0000 <p>Mechanical interlocking has recently emerged as a novel structural design principle for crystalline porous organic materials. Unlike traditional reticular chemistry that relies on covalent or coordination bonding to build rigid lattices, mechanical bonding provides an alternative design space where the structural integrity of the crystal is maintained while the individual components preserve intrinsic mobility. The incorporation of interlocked macrocycles, cages, and framework subunits has enabled new forms of structural order that combine crystallinity with dynamic molecular motion. This review summarizes current progress in the synthesis and structural design of crystalline porous materials driven by topology interlocking. The discussion is organized by increasing structural hierarchy, covering interlocked macrocycles, interlocked cages, mechanically interlocked metal-organic frameworks, and interlocked covalent organic frameworks. The relationships between interlocking geometry, structural organization, and application area are highlighted. The review concludes with an outlook on the opportunities and challenges associated with mechanical bonding as a programmable element in crystalline porous materials.</p>\u0000 \u0000 <p>\u0000 </p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Key Scientists</h3>\u0000 \u0000 <p>A brief overview of the leading contributors in the field highlights how topology interlocking has become a powerful design principle for crystalline porous materials. Foundational insights were provided by Sauvage and Stoddart in the 1980s, whose studies on mechanically bonded molecules and molecular machines significantly promoted the development of mechanically interlocked molecules. Fujita advanced the field by showing that metal-directed self-assembly can spontaneously produce catenated metal-organic cages (MOCs) and macrocycles, while Cooper demonstrated that catenated organic cages can arise through dynamic covalent chemistry without metal templates. Mechanical interlocking was extended to frameworks by Yaghi, who realized woven covalent organic frameworks (COFs), and by Loh, who introduced rotaxane-based COFs with engineered interlayer behavior. Aida and Sato reported the first metal-organic frameworks constructed from a catenated polymer backbone. Most recently, Cui and co-workers first reported an interlocked metal peptide macrocycle and hetero-interlocked MOC. Important contributions from Jin and Guido Clever expanded the scope of interlocked macrocycles and MOCs, respectively. Collectively, these achievements established the foundation of topology interlocked crystalline porous materials.</p>\u0000 \u0000 <p>\u0000 </p>\u0000 </section>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 16","pages":"2791-2805"},"PeriodicalIF":5.7,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148533288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}