CCS Chemistry最新文献

{"title":"Enantioselective Synthesis and Characterization of Strained [8]–[9]Paracyclophanes","authors":"Jia Li, Ziyang Dong, Chang Yuan, Changgui Zhao","doi":"10.31635/ccschem.026.202607590","DOIUrl":"https://doi.org/10.31635/ccschem.026.202607590","url":null,"abstract":"The introduction of strain into paracyclophanes offers fundamental insights into aromaticity and molecular properties. However, the asymmetric synthesis of strained [n]paracyclophanes (n ≤ 9) has been scarcely explored. In this study, a highly enantioselective synthesis of [8]- and [9]paracyclophanes is accomplished via a sequential strategy involving Suzuki macrocyclization and palladium-catalyzed C–H olefination. The success of the macrocyclization is attributed to the ring contraction of a proposed palladium-containing paracyclophane intermediate formed during the Suzuki coupling process. Density functional theory calculations elucidate the influence of ring strain and diminished aromaticity on enantiocontrol in the C–H activation step. Further photophysical and theoretical studies correlate ring size with the evolution of photophysical properties, structural distortion, and aromaticity. Additionally, nuclear magnetic resonance spectroscopy, together with the isosurface of the ZZ component of the iso-chemical shielding surface (ICSS_ZZ), reveals a clear correlation between the observed anisotropic shielding effects and the degree of structural distortion.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"4 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147611865","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":"Electrocatalytic C(sp3)–H/S–H Coupling: Accessing Thioethers via a Stabilized Electrophile","authors":"Yousen Xu, Chenxi Zhu, Jiangju Luo, Lei Zhang","doi":"10.31635/ccschem.026.202607499","DOIUrl":"https://doi.org/10.31635/ccschem.026.202607499","url":null,"abstract":"The electrochemical C(sp³)–H/S–H coupling of thiols is an atom-economical approach to accessing thioethers but remains challenging due to competing thiol over-oxidation. Herein, we report a strategy that circumvents these limitations by employing a quinoline mediator to generate stabilized electrophilic fluoroalkoxyl intermediates, which undergo nucleophilic substitution with electron-rich thiols to form C(sp³)–S bonds efficiently. Replacing hexafluoroisopropanol (HFIP) with trifluoroethanol (TFE) enables the activation of tertiary and allylic C–H bonds. This protocol accommodates a broad substrate scope across diverse C–H coupling partners and thiols. It demonstrates significant utility through successful scaling in continuous flow, late-stage functionalization of complex molecules, and concise synthesis of sulconazole. This strategy is further generalizable to other electron-rich nucleophiles, including dialkyl amines, providing an oxidant-free route to the formation of C(sp³)–C and C(sp³)–N bonds.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"64 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147611866","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":"Reticular Chemistry with π-Extended PrismCage Building Units","authors":"Le Shi, Zhijie Chen","doi":"10.31635/ccschem.026.202607596","DOIUrl":"https://doi.org/10.31635/ccschem.026.202607596","url":null,"abstract":"The precise control of building units in porous reticular solids is of great importance for fine-tuning their functionalities. However, it remains challenging to systematically tune pore structures using π-extended molecular building units to enhance molecular recognition. Herein, we report the reticular synthesis of a zirconium-based metal-organic framework (Zr-MOF)—Zr-PC-1-<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>nia</bold></b>, assembled from zirconium oxo-clusters and ligands containing oxygen-bridged trigonal prism-shaped organic cage (PrismCage). Subsequently, the isoreticular frameworks Zr-PC-2-<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>nia</bold></b> and Zr-PC-3-<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>nia</bold></b> were rationally synthesized by employing state-of-the-art reticular chemistry that incorporates π-extended PrismCage building units. The tunable supramolecular host-guest interactions inherent to the PrismCage building units within the framework offer potential for selective molecular recognition, as evidenced by the enhanced interaction of adsorbed iodine (I₂) with Zr-PC-3-<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>nia</bold></b> over Zr-PC-2-<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>nia</bold></b> due to the simple modification of central electron-rich benzene cores with electron-deficient triazine cores. Our finding paves the way for the reticular design of functional hierarchical periodic frameworks through the integration of supramolecular-host-based building units—π-extended PrismCage linkers.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"27 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147611867","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":"Transmuting Zirconium Metal-Organic Framework through Precise Molecular Retrofitting for Benchmark Batch and Flow-Through Iodine Capture from Water","authors":"Yuan Geng, Jingjing Zhang, Pengfu Gao, Ji Guo, Yifei Gao, Yong Cui, Wei Gong","doi":"10.31635/ccschem.026.202607381","DOIUrl":"https://doi.org/10.31635/ccschem.026.202607381","url":null,"abstract":"Precise post-synthetic linker installation in metal-organic frameworks (MOFs) lattices—molecular retrofitting—offers an exceptionally powerful approach to reform the porous architectures and manipulate the macroscopic physiochemical properties. In this work, inspired by the delicate cantellation design strategy that leads to conformation “locked” Zr₆ molecular building blocks (MBBs) with triple linker bridges, we show that the prototypical Zr-MOF (NU-1200/BUT-12) can be readily retrofitted by precise placement of congenetic bent linkers as the third bridge via perfect geometric complementarity. This retrofitting gives rise to two isostructural frameworks with intricate augmented topology and results in a remarkable enhancement of chemical stability and mechanical robustness as well as an increase of surface area and micropore volume. The retrofitted Zr-MOF decorated with deliberately introduced pyridine functionality demonstrates benchmark efficiency toward direct iodine capture from water, across a broad pH range from 1 to 11, under both batch and flow-through conditions. Our findings demonstrate retrofitting as a powerful approach capable of reinventing reticular materials via rational design, and formulate principles to fine-tune structures and properties in this versatile class of materials.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"5 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147611877","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":"Asymmetric Synthesis and Skeletal Isomerization of Strained Cycloalkenes via trans-Selective Higher-Order Cycloaddition","authors":"Jin-Pu Zhao, Fang Hu, Jun-Wei Shi, Meng Xiao, Bin Shi, Xue-Rui Wang, Ying Tan, Li-Yan Chen, Zhihan Zhang, Wen-Jing Xiao, Liang-Qiu Lu","doi":"10.31635/ccschem.026.202607340","DOIUrl":"https://doi.org/10.31635/ccschem.026.202607340","url":null,"abstract":"Cycloalkenes are pivotal structural cores in many bioactive molecules, yet the catalytic asymmetric synthesis of their medium-sized <i>trans</i>-isomers remains formidable due to high ring strain and stereocontrol challenges. To address this issue, we report a palladium-catalyzed asymmetric (7+4) cycloaddition that efficiently produces strained 11-membered chiral <i>trans</i>-cycloalkenes. This modular strategy assembles π-allyl-Pd 1,7-dipoles and azadienes, affording the core structures with high yield and exceptional stereocontrol (33 examples, up to 97% yield, &gt;19:1 <i>trans</i>/<i>cis</i>, &gt;19:1 dr, and &gt;99% ee). Importantly, the inherent strain is repurposed as a strategic tool for diversifying the molecular structure: it enables enantiospecific access to the corresponding <i>cis</i>-isomers via alkene isomerization and to chiral bispirocycles via cascade ring-contraction reactions. Consequently, our work establishes a versatile platform for accessing elusive <i>trans</i>-cycloalkene architectures and demonstrates their utility in strain-driven skeletal isomerization.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"16 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147611884","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":"Backbone Elongation as a Molecular Lever for Horizontal Dipole Orientation in TSCT-TADF Emitters","authors":"Qi Zheng, Dong-Ying Zhou, Hai-Tian Yuan, Yue-Jian Yang, Yu-Chen Qiu, Yang-Kun Qu, Liang-Sheng Liao, Zuo-Quan Jiang","doi":"10.31635/ccschem.026.202607301","DOIUrl":"https://doi.org/10.31635/ccschem.026.202607301","url":null,"abstract":"Through-space charge-transfer thermally activated delayed fluorescence (TSCT-TADF) emitters have emerged as a promising class of OLED materials owing to their near-unity exciton utilization efficiency. As excited-state engineering in TSCT systems has approached its intrinsic efficiency limit, further improvements in device performance increasingly rely on enhancing light-outcoupling efficiency. Here, we demonstrate a molecular design strategy to facilitate horizontal dipole orientation by elongating the molecular backbone through multi-spiro engineering. Two elongated TSCT-TADF emitters were developed as derivatives of the benchmark spiro-based system, preserving the rigid cofacial donor-acceptor configuration and emissive TSCT excited state. Single-crystal analysis reveals that backbone elongation enforces rigid and anisotropic molecular geometries and induces anisotropic packing motifs governed by weak intermolecular interactions. As a result, the elongated emitters exhibit significantly enhanced horizontal dipole orientation in vacuum-deposited thin films. OLED devices incorporating these emitters show improved external quantum efficiency without altering emission color, highlighting orientation-driven light-outcoupling enhancement as an effective pathway beyond excited-state optimization. This work establishes backbone elongation as a general molecular strategy for regulating dipole orientation and advancing high-efficiency TSCT-based OLEDs.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"2 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147625492","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":"Protection-Free Synthesis of Multiclickable Polymethacrylate Bearing Acetylene and Vinyl Groups via Living Lewis Pair Polymerization","authors":"Huaiyu Wang, Wuchao Zhao, Jianghua He, Yuetao Zhang","doi":"10.31635/ccschem.025.202505808","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505808","url":null,"abstract":"Acetylene- and vinyl-containing polymers are versatile platforms for the production of multifunctional polymer materials. However, poor control and incomplete retention of vinyl and acetylene groups are often rendered by current polymerization techniques as both of these groups are either incompatible with reaction conditions or involved in polymerization and/or chain transfer reaction. Here, an organophosphorus-based Lewis pair is employed to achieve living/controlled and completely chemoselective polymerization of 3-butynyl methacrylate under mild conditions, furnishing soluble polymers bearing acetylene groups with adjustable molecular weight (<i>M</i>_n = 14.7–322 kg/mol). The living feature of Lewis pair polymerization enables the successful chain extension and block copolymerization experiments. When divinyl monomer is used as a comonomer, acetylene and vinyl groups can be introduced into the polymers with desired distribution density and position, simply by changing the comonomer ratio and feeding order. By selecting appropriate reactions, such as the Cu(I) catalyzed azide-alkyne cycloaddition click reaction and photoinduced addition reaction, multiple reactive sites could be separately modified to introduce different dynamic bonds and interactions into polymer networks, furnishing self-healing material.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"274 1","pages":"1-29"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147599399","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":"Directed Cocatalyst Deposition on Organic Semiconductor Heterojunctions to Boost Photocatalytic Hydrogen Production","authors":"Qi Zhao, Kun Tang, Jiang-Yang Shao, Chang He, Yongli Yan, Jikun Li, Can Yu, Jiannian Yao, Yu-Wu Zhong","doi":"10.31635/ccschem.025.202505751","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505751","url":null,"abstract":"Organic semiconductors and heterojunctions have recently received considerable interest as molecular catalysts for energy-related photoconversion, in which metal cocatalysts are often incorporated to enhance their activity. In these processes, the manner of the cocatalyst deposition is believed to play a crucial role in influencing its activity, though this issue has been largely overlooked until now. In this work, we present the use of a bifunctional small molecule, 1,3,6,8-tetra(di(<i>p</i>-pyrid-4-yl-phenyl)amino)pyrene (TAPyr), to address this issue. TAPyr is not only able to form heterojunctions with graphitic carbon nitride (CN) through potential π–π and hydrogen bond interactions but also to create pyridine-rich surfaces to direct the Pt cocatalyst deposition in a discrete and small-scale manner. This heterojunction photocatalyst exhibits a maximum hydrogen evolution rate of 6.6 mmol·h⁻¹·g_cat⁻¹ (based on 50 mg of catalyst used) under visible light, corresponding to an apparent rate of 660 mmol·h⁻¹·g_Pt⁻¹ normalized to the added Pt precursor (1 wt %, 0.5 mg Pt) with an excellent photocatalytic stability and recyclability. The beneficial role of the directed cocatalyst deposition in boosting the photocatalytic hydrogen production is supported by control experiments using a pyridine-free analog and theoretical calculations on the Pt deposition processes.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"40 1","pages":"1-38"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147620412","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":"Accelerated Bidirectional Photochromism via Excited Bridge","authors":"Jin-Ai Fan, Hao Yu, Xu-Ying Yu, Wei-Chao Yang, Cai Sun, Shou-Tian Zheng","doi":"10.31635/ccschem.025.202506871","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506871","url":null,"abstract":"The bridge connecting the electron donor and acceptor is crucial for electron transfer (ET). However, the impact of the excited bridge on this process remains unclear. Here, we establish a proof-of-concept model based on an ET photochromic polyoxoniobate containing an f-type bridge, through which the effect of the excited bridge on ET is systematically studied. The excited bridge significantly accelerates the coloration rate of a 1.7-fold. Colored samples also exhibit accelerated bleaching through the excited bridge, marking the first instance of light-assisted acceleration of reverse ET, which was previously constrained in the thermal mode. The light-assisted bleaching rate is approximately 494 times faster than the traditional thermal mode at room temperature, leading to a significant reduction in the half-life from 91.58 min to 11.13 s. The study identifies the primary cause of the increased response to be the significant enhancement in electronic coupling between the initial and colored states by the excited bridge. This intriguing photochromic behavior not only opens new applications for multifactor anticounterfeiting but also initiates research into the excited bridges.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"17 1","pages":"1-8"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147620413","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":"Direct Measurement of a Sequence of Quantized Bottleneck States in the H + HD(v = 1) → H2 + D Reaction","authors":"Yurun Xie, Wei Wang, Yufeng Wang, Zhaojun Zhang, Bin Zhao, Shu Liu, Chunlei Xiao, Dong H. Zhang, Xueming Yang","doi":"10.31635/ccschem.026.202507132","DOIUrl":"https://doi.org/10.31635/ccschem.026.202507132","url":null,"abstract":"Quantized bottleneck states (QBSs) are a series of quantum states associated with reaction barriers that, similar to Feshbach resonance states, can influence physical observables. However, although the existence of QBSs has been experimentally confirmed, direct measurement of their sequences has not yet been achieved. In this work, we present a combined high-resolution crossed-beam scattering and quantum dynamical study of the H + HD(<i>v</i> = 1, <i>j</i> = 0) → H₂ + D reaction and successfully extract the vibrational energy levels of QBSs [i.e., the barrier heights of the vibrationally adiabatic potential (VAP)] from the oscillatory structures in the product rovibrationally state-resolved backward scattering spectrum (BSS). Each peak in the reaction probabilities and BSS is assigned to a specific QBS, including the QBSs associated with the lower barrier on the reactant side of the symmetric-stretch-excited VAP that have not been observed previously. This work provides a direct probe of the structure in the transition state region and demonstrates that the QBSs involved in a reaction are dependent on the initial state.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"64 1","pages":"1868-1876"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147599376","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}