Accurately measuring cation-π interactions in solution is challenging due to their highly dynamic and transient nature that hinders our understanding of their effects on molecular properties. In this study, we revisit established paradigms of cation-π interaction by employing a bioinspired molecular host with a confined space, designed to stabilize and consequently clearly observe these subtle interactions in solution. By incorporating fluorine atoms as sensitive reporters, we uncovered unusual confinement-induced trends in which larger cations induced stronger perturbations in the electronic environment of the π-system. This finding differs from traditional gas-phase observations and computational simulations in bulk aqueous solutions. Using 19F NMR spectroscopy, we quantified these unusual trends and demonstrated their direct correlation with control over molecular reactivity, as exemplified by the regulated solvolysis rate of a model compound. Our results refine the current understanding of cation-π interactions and offer new insights for the rational design of catalysts and smart materials through the precise manipulation of noncovalent interactions.
{"title":"Revisiting Cation-π Interaction Paradigms: Unusual Confinement-Induced Trends and Implications for Reactivity Control","authors":"Zhenchuang Xu, Wenjie Zhu, Jian Wu, Wei Zhang, Yanchuan Zhao","doi":"10.31635/ccschem.025.202506222","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506222","url":null,"abstract":"Accurately measuring cation-π interactions in solution is challenging due to their highly dynamic and transient nature that hinders our understanding of their effects on molecular properties. In this study, we revisit established paradigms of cation-π interaction by employing a bioinspired molecular host with a confined space, designed to stabilize and consequently clearly observe these subtle interactions in solution. By incorporating fluorine atoms as sensitive reporters, we uncovered unusual confinement-induced trends in which larger cations induced stronger perturbations in the electronic environment of the π-system. This finding differs from traditional gas-phase observations and computational simulations in bulk aqueous solutions. Using <sup>19</sup>F NMR spectroscopy, we quantified these unusual trends and demonstrated their direct correlation with control over molecular reactivity, as exemplified by the regulated solvolysis rate of a model compound. Our results refine the current understanding of cation-π interactions and offer new insights for the rational design of catalysts and smart materials through the precise manipulation of noncovalent interactions.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"36 2 1","pages":"1-12"},"PeriodicalIF":11.2,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731746","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}
Pub Date : 2025-12-11DOI: 10.31635/ccschem.025.202506960
Bin Wei, Jiangtao Wang, Lihan Zhu, Xiao-Xi Li, Kehan Jiao, Jichao Xiao, Guangfan Zheng, Xingwei Li
Chiral sulfilimines, the aza-analogues of sulfoxides, represent versatile synthetic intermediates and privileged structural motifs found in various bioactive molecules. Nevertheless, the catalytic enantioselective synthesis of sulfilimines remains a formidable challenge. While asymmetric S-functionalization of sulfenamides offers an attractive alternative, previous methodologies have predominantly relied on polar mechanisms with preactivated coupling partners. Herein, we report a direct and robust strategy for the asymmetric construction of chiral sulfilimines via copper-catalyzed enantioselective remote benzylic C–H sulfilimination of N-fluorocarboxamides using readily accessible sulfenamides as both sulfur and nitrogen sources. The success of this approach relay on the formation of a Cu–sulfinimidoyl intermediate through S(II)/S(IV) tautomerization, which facilitates single-electron reduction of the N-fluorocarboxamide followed by an enantio-determining C–S bond formation. Furthermore, cyclobutanone oxime esters are also compatible substrates under this newly developed protocol, enabling enantioselective remote sulfilimination via iminyl radical-induced β-C–C bond cleavage. This methodology constitutes the first example of enantioselective C–H or C–C sulfilimination via a radical pathway, offering a complementary and orthogonal alternative to conventional polar mechanisms, thereby establishing a new paradigm in asymmetric sulfilimination chemistry.
{"title":"Copper-Catalyzed Asymmetric Sulfilimination of Diverse Radical Precursors via Nitrogen-Centered Radical-Enabled C–H and C–C Cleavage","authors":"Bin Wei, Jiangtao Wang, Lihan Zhu, Xiao-Xi Li, Kehan Jiao, Jichao Xiao, Guangfan Zheng, Xingwei Li","doi":"10.31635/ccschem.025.202506960","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506960","url":null,"abstract":"Chiral sulfilimines, the aza-analogues of sulfoxides, represent versatile synthetic intermediates and privileged structural motifs found in various bioactive molecules. Nevertheless, the catalytic enantioselective synthesis of sulfilimines remains a formidable challenge. While asymmetric S-functionalization of sulfenamides offers an attractive alternative, previous methodologies have predominantly relied on polar mechanisms with preactivated coupling partners. Herein, we report a direct and robust strategy for the asymmetric construction of chiral sulfilimines <i>via</i> copper-catalyzed enantioselective remote benzylic C–H sulfilimination of <i>N</i>-fluorocarboxamides using readily accessible sulfenamides as both sulfur and nitrogen sources. The success of this approach relay on the formation of a Cu–sulfinimidoyl intermediate through S(II)/S(IV) tautomerization, which facilitates single-electron reduction of the <i>N</i>-fluorocarboxamide followed by an enantio-determining C–S bond formation. Furthermore, cyclobutanone oxime esters are also compatible substrates under this newly developed protocol, enabling enantioselective remote sulfilimination <i>via</i> iminyl radical-induced β-C–C bond cleavage. This methodology constitutes the first example of enantioselective C–H or C–C sulfilimination via a radical pathway, offering a complementary and orthogonal alternative to conventional polar mechanisms, thereby establishing a new paradigm in asymmetric sulfilimination chemistry.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"118 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145759458","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}
The synthesis of nonbenzenoid nanographenes (NGs) with a high density of nonhexagonal rings remains a significant challenge, leaving this structural class largely unexplored. In this work, we report the efficient synthesis of a novel nonbenzenoid isomer of decacyclene, namely cyclopenta[cd]azulene trimer (CPAT), derived from the natural product guaiazulene. The key step involves an acid–base buffer-assisted cyclotrimerization of cyclopenta[cd]azulen-2(1H)-one that can be further extended to produce halogenated derivative, enabling structural tunability. The resulting molecules feature a unique backbone comprising nine nonhexagonal rings arranged around a central benzenoid core, representing the highest pentagon–heptagon ring density among all reported π-extended NGs with ten or more fused rings. Compared to the pristine decacyclene, the synthesized compounds exhibit excellent ambient stability, narrower bandgaps, and distinct aromaticity profiles. Moreover, femtosecond transient absorption measurements of CPAT-a reveal an ultrafast singlet-state relaxation (∼14 ps), significantly shorter than that of decacyclene, highlighting the pronounced impact of nonbenzenoid topology on excited-state dynamics. This study introduces a new family of nonbenzenoid NGs and paves the way for the synthesis of new sp2 carbon allotrope featuring exclusively nonhexagonal ring systems.
{"title":"Cyclopenta[cd]azulene Trimer: A Unique Nonbenzenoid Nanographene with High Pentagon-Heptagon Density","authors":"Renxiang Liu, Xin Zhou, Yubin Fu, Fupin Liu, Fupeng Wu, Qiang Huang, Alexey A. Popov, Yungui Li, Ji Ma, Xinliang Feng","doi":"10.31635/ccschem.025.202506462","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506462","url":null,"abstract":"The synthesis of nonbenzenoid nanographenes (NGs) with a high density of nonhexagonal rings remains a significant challenge, leaving this structural class largely unexplored. In this work, we report the efficient synthesis of a novel nonbenzenoid isomer of decacyclene, namely cyclopenta[<i>cd</i>]azulene trimer (<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>CPAT</bold></b>), derived from the natural product guaiazulene. The key step involves an acid–base buffer-assisted cyclotrimerization of cyclopenta[<i>cd</i>]azulen-2(<i>1H</i>)-one that can be further extended to produce halogenated derivative, enabling structural tunability. The resulting molecules feature a unique backbone comprising nine nonhexagonal rings arranged around a central benzenoid core, representing the highest pentagon–heptagon ring density among all reported π-extended NGs with ten or more fused rings. Compared to the pristine decacyclene, the synthesized compounds exhibit excellent ambient stability, narrower bandgaps, and distinct aromaticity profiles. Moreover, femtosecond transient absorption measurements of <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>CPAT-a</bold></b> reveal an ultrafast singlet-state relaxation (∼14 ps), significantly shorter than that of decacyclene, highlighting the pronounced impact of nonbenzenoid topology on excited-state dynamics. This study introduces a new family of nonbenzenoid NGs and paves the way for the synthesis of new sp<sup>2</sup> carbon allotrope featuring exclusively nonhexagonal ring systems.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"4 1","pages":"1-10"},"PeriodicalIF":11.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145746686","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}
Conjugating tumor antigens to nanocarriers can enhance the antitumor immune activity of the carriers. However, nanocarriers can uncontrollably interact with serum proteins during systemic circulation, which hinders the precise capture of tumor antigens. Here, we present ultrasound-responsive sono-switch nanocatchers (S-nanocatchers) that enable spatiotemporally controlled in situ tumor antigen capture. The S-nanocatchers are composed of poly(l-glutamic acid) integrated with a thioether-containing antigen-capturing group and the sonosensitizer pyropheophorbide a (PPa). Upon self-assembly, the hydrophobic antigen-capturing group and PPa remained encapsulated in the core. Upon ultrasound exposure, PPa-mediated reactive oxygen species generation induced immunogenic cell death of the tumor and oxidizes thioether to hydrophilic sulfone/sulfoxide, thereby transforming the antigen-capturing group on the nanoparticle surface and enabling in situ covalent capture of tumor antigens. Control nanocatchers (C-nanocatchers) containing carbon-substituted linkers exhibited negligible antigen-binding capacity with ultrasound irradiation, which confirmed that the switch mechanism is sulfur oxidation-dependent. This study presents a pioneering precision strategy that bridges ultrasound-guided capture with on-demand vaccine synthesis. The strategy could be applied in adaptive material design for personalized cancer immunotherapy.
{"title":"Sono-Switch Nanocatchers for Spatiotemporally Controlled In Situ Tumor Antigen Capture","authors":"Linjie Cui, Yanfei Song, Xitong Ren, Weidong Zhao, Lili Ma, Zhilin Liu, Zhaohui Tang, Xuesi Chen","doi":"10.31635/ccschem.025.202506686","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506686","url":null,"abstract":"Conjugating tumor antigens to nanocarriers can enhance the antitumor immune activity of the carriers. However, nanocarriers can uncontrollably interact with serum proteins during systemic circulation, which hinders the precise capture of tumor antigens. Here, we present ultrasound-responsive sono-switch nanocatchers (S-nanocatchers) that enable spatiotemporally controlled in situ tumor antigen capture. The S-nanocatchers are composed of poly(<span>l</span>-glutamic acid) integrated with a thioether-containing antigen-capturing group and the sonosensitizer pyropheophorbide a (PPa). Upon self-assembly, the hydrophobic antigen-capturing group and PPa remained encapsulated in the core. Upon ultrasound exposure, PPa-mediated reactive oxygen species generation induced immunogenic cell death of the tumor and oxidizes thioether to hydrophilic sulfone/sulfoxide, thereby transforming the antigen-capturing group on the nanoparticle surface and enabling in situ covalent capture of tumor antigens. Control nanocatchers (C-nanocatchers) containing carbon-substituted linkers exhibited negligible antigen-binding capacity with ultrasound irradiation, which confirmed that the switch mechanism is sulfur oxidation-dependent. This study presents a pioneering precision strategy that bridges ultrasound-guided capture with on-demand vaccine synthesis. The strategy could be applied in adaptive material design for personalized cancer immunotherapy.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"22 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731802","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}
Pub Date : 2025-12-10DOI: 10.31635/ccschem.025.202506382
Kai Zhang, Wanjun Shi, Wenting Liang, Ren Su
Photocatalysis employing framework-based materials has attracted extensive attention in hydrogen evolution, carbon dioxide reduction, and synthetic chemistry. Precise functionalization of the framework photocatalysts is the key to optimizing light absorption, charge separation, and surface reaction kinetics to achieve satisfactory catalytic performances. In this review, we summarized strategies and progress in photocatalytic energy and chemical conversions using metal–organic frameworks, covalent–organic frameworks, and hydrogen-bonded organic frameworks, from the perspective of assembly components and applications. The construction of composites and heterostructures with metal cocatalysts and conventional semiconductors is also discussed. The promotional mechanisms of functionalization are discussed to provide strategies for energy conversion and chemical synthesis-oriented designs of framework photocatalysts. The limitations and challenges for further development of framework-based photocatalysis, including applications at practical scales, characterizations of dynamic structural evolution, and appropriate reports of catalytic performances for artificial intelligence-aided design are elaborated.
{"title":"Functionalized Framework Materials for Light-Driven Energy and Chemical Conversions","authors":"Kai Zhang, Wanjun Shi, Wenting Liang, Ren Su","doi":"10.31635/ccschem.025.202506382","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506382","url":null,"abstract":"Photocatalysis employing framework-based materials has attracted extensive attention in hydrogen evolution, carbon dioxide reduction, and synthetic chemistry. Precise functionalization of the framework photocatalysts is the key to optimizing light absorption, charge separation, and surface reaction kinetics to achieve satisfactory catalytic performances. In this review, we summarized strategies and progress in photocatalytic energy and chemical conversions using metal–organic frameworks, covalent–organic frameworks, and hydrogen-bonded organic frameworks, from the perspective of assembly components and applications. The construction of composites and heterostructures with metal cocatalysts and conventional semiconductors is also discussed. The promotional mechanisms of functionalization are discussed to provide strategies for energy conversion and chemical synthesis-oriented designs of framework photocatalysts. The limitations and challenges for further development of framework-based photocatalysis, including applications at practical scales, characterizations of dynamic structural evolution, and appropriate reports of catalytic performances for artificial intelligence-aided design are elaborated.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"10 1","pages":"1-35"},"PeriodicalIF":11.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731798","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}
Pub Date : 2025-12-10DOI: 10.31635/ccschem.025.202506624
Ya-Liang Lai, Xue-Zhi Wang, Ye-Ting Wang, Hu Yang, Xian-Chao Zhou, Hao-Jie Zhang, Chuang-Wei Zhou, Dong Luo, Xiao-Ping Zhou, Dan Li
Mimicking allosteric regulation in artificial systems could enable the development of highly responsive and adaptive materials and devices. Herein, we described a strategy for controlling the architecture of metal–organic helicates using K+ ions as allosteric effectors and 18-crown-6 units as allosteric binding sites, thereby allowing for simultaneous regulation of cavity formation and host–guest chemistry. The self-assembly of the flexible crown ether-based diamine and 2-formylpyridine subcomponents around the Zn(II) templates afforded a Zn2L3 mesocate structure, with two ZnII centers adopting fac-ΔΛ configurations. Upon binding K+ ions, a dinuclear Zn2L3K3 helicate was formed in which the ZnII centers maintained fac-ΔΔ or ΛΛ stereochemistry. This stereochemical change led to a markedly different anion-binding behavior between Zn2L3 and Zn2L3K3. In the Zn2L3 structure, anions remain free, whereas Zn2L3K3 selectively encapsulates oxygen-containing anions (NO3−, ClO4−, and OTf−), displaying the highest binding constant of 4.89 × 105 M−1 for NO3−. These structures could be reversibly switched between Zn2L3 and Zn2L3K3 through the addition or removal of K+ ions, thereby modulating anion binding and providing a robust artificial model of biological allosteric regulation. Furthermore, chiral anions (l-/d-camphor sulfonate) could induce the formation of homochiral fac-ΔΔ or fac-ΛΛ helicates by determining the vertex stereochemistry.
{"title":"Control of Anion Binding in Metal–Organic Helicates via Allosteric Regulation","authors":"Ya-Liang Lai, Xue-Zhi Wang, Ye-Ting Wang, Hu Yang, Xian-Chao Zhou, Hao-Jie Zhang, Chuang-Wei Zhou, Dong Luo, Xiao-Ping Zhou, Dan Li","doi":"10.31635/ccschem.025.202506624","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506624","url":null,"abstract":"Mimicking allosteric regulation in artificial systems could enable the development of highly responsive and adaptive materials and devices. Herein, we described a strategy for controlling the architecture of metal–organic helicates using K<sup>+</sup> ions as allosteric effectors and 18-crown-6 units as allosteric binding sites, thereby allowing for simultaneous regulation of cavity formation and host–guest chemistry. The self-assembly of the flexible crown ether-based diamine and 2-formylpyridine subcomponents around the Zn(II) templates afforded a Zn<sub>2</sub>L<sub>3</sub> mesocate structure, with two Zn<sup>II</sup> centers adopting <i>fac</i>-ΔΛ configurations. Upon binding K<sup>+</sup> ions, a dinuclear Zn<sub>2</sub>L<sub>3</sub>K<sub>3</sub> helicate was formed in which the Zn<sup>II</sup> centers maintained <i>fac</i>-ΔΔ or ΛΛ stereochemistry. This stereochemical change led to a markedly different anion-binding behavior between Zn<sub>2</sub>L<sub>3</sub> and Zn<sub>2</sub>L<sub>3</sub>K<sub>3</sub>. In the Zn<sub>2</sub>L<sub>3</sub> structure, anions remain free, whereas Zn<sub>2</sub>L<sub>3</sub>K<sub>3</sub> selectively encapsulates oxygen-containing anions (NO<sub>3</sub><sup>−</sup>, ClO<sub>4</sub><sup>−</sup>, and OTf<sup>−</sup>), displaying the highest binding constant of 4.89 × 10<sup>5</sup> M<sup>−1</sup> for NO<sub>3</sub><sup>−</sup>. These structures could be reversibly switched between Zn<sub>2</sub>L<sub>3</sub> and Zn<sub>2</sub>L<sub>3</sub>K<sub>3</sub> through the addition or removal of K<sup>+</sup> ions, thereby modulating anion binding and providing a robust artificial model of biological allosteric regulation. Furthermore, chiral anions (<span>l</span>-/<span>d</span>-camphor sulfonate) could induce the formation of homochiral <i>fac</i>-ΔΔ or <i>fac</i>-ΛΛ helicates by determining the vertex stereochemistry.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"147 1","pages":"1-10"},"PeriodicalIF":11.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731800","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}
Pub Date : 2025-12-10DOI: 10.31635/ccschem.025.202506276
Lifei Xu, Ying Pan, Han-Xiao Wang, Minghua Liu
The chirality-match-directed self-sorting behavior in artificial supramolecular multicomponent systems represents a fascinating research frontier due to its fundamental relevance to chiral selection in biological processes. In this work, we demonstrate chirality-match-governed switching between narcissistic and social self-sorting pathways, enabling selective generation of either excimer or exciplex circularly polarized luminescence (CPL). By covalently tethering an amphiphilic chiral glutamide moiety to two distinct π-conjugated headgroups—pyrene and N,N-dimethylaniline—we designed a pair of chiral amphiphiles capable of coassembling into two-component assemblies (TCA). Spectroscopic investigations revealed that the formation of TCA in ethyl acetate facilitated chirality-dependent switching between exciplex and excimer states, each exhibiting distinct fluorescence (FL) and CPL signatures. Specifically, narcissistic self-sorting led to the formation of chiral excimers with characteristic FL and CPL profiles, whereas social self-sorting produced chiral exciplexes with markedly different spectral features. These findings were systematically corroborated using multiple analytical techniques. This study presents the first experimental demonstration of steering excited-state chiral excimers/exciplexes through molecular chirality matching, thereby establishing new design principles for advanced chiroptical materials.
{"title":"Chirality-Match-Directed Narcissistic Versus Social Self-Sorting for Selective Excimer or Exciplex Circularly Polarized Luminescence","authors":"Lifei Xu, Ying Pan, Han-Xiao Wang, Minghua Liu","doi":"10.31635/ccschem.025.202506276","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506276","url":null,"abstract":"The chirality-match-directed self-sorting behavior in artificial supramolecular multicomponent systems represents a fascinating research frontier due to its fundamental relevance to chiral selection in biological processes. In this work, we demonstrate chirality-match-governed switching between narcissistic and social self-sorting pathways, enabling selective generation of either excimer or exciplex circularly polarized luminescence (CPL). By covalently tethering an amphiphilic chiral glutamide moiety to two distinct π-conjugated headgroups—pyrene and <i>N</i>,<i>N</i>-dimethylaniline—we designed a pair of chiral amphiphiles capable of coassembling into two-component assemblies (TCA). Spectroscopic investigations revealed that the formation of TCA in ethyl acetate facilitated chirality-dependent switching between exciplex and excimer states, each exhibiting distinct fluorescence (FL) and CPL signatures. Specifically, narcissistic self-sorting led to the formation of chiral excimers with characteristic FL and CPL profiles, whereas social self-sorting produced chiral exciplexes with markedly different spectral features. These findings were systematically corroborated using multiple analytical techniques. This study presents the first experimental demonstration of steering excited-state chiral excimers/exciplexes through molecular chirality matching, thereby establishing new design principles for advanced chiroptical materials.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"1 1","pages":"1-12"},"PeriodicalIF":11.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145746678","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}
Pub Date : 2025-12-10DOI: 10.31635/ccschem.025.202506397
Jiantao Zhao, Huacheng Yu, Jiang-Fei Xu, Xi Zhang
Click–clip reactions are an emerging field that integrates efficient bond formation (“click”) with selective and controllable bond cleavage (“clip”), enabling reversible molecular linking under mild and precisely controlled conditions. This mini-review provides an overview of recent developments in click–clip reactions, emphasizing their significance in creating stable but controllably reversible molecular systems. It covers essential concepts including reaction design principles, mechanisms of bond cleavage, and strategies for triggering these reversible processes. By highlighting the inherent advantages and versatility of click–clip approaches, this review underscores their potential to construct dynamic materials, adaptable polymers, and responsive biomolecules whose functions can be turned on or off. Despite significant advancements, several challenges remain and require ongoing investigation, including efficiency, specificity, and biocompatibility. The importance of connecting real challenges of materials and drugs with click–clip reactions research is highly anticipated, thereby contributing to precise and sustainable chemistry.
{"title":"On Click–Clip Reactions","authors":"Jiantao Zhao, Huacheng Yu, Jiang-Fei Xu, Xi Zhang","doi":"10.31635/ccschem.025.202506397","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506397","url":null,"abstract":"Click–clip reactions are an emerging field that integrates efficient bond formation (“click”) with selective and controllable bond cleavage (“clip”), enabling reversible molecular linking under mild and precisely controlled conditions. This mini-review provides an overview of recent developments in click–clip reactions, emphasizing their significance in creating stable but controllably reversible molecular systems. It covers essential concepts including reaction design principles, mechanisms of bond cleavage, and strategies for triggering these reversible processes. By highlighting the inherent advantages and versatility of click–clip approaches, this review underscores their potential to construct dynamic materials, adaptable polymers, and responsive biomolecules whose functions can be turned on or off. Despite significant advancements, several challenges remain and require ongoing investigation, including efficiency, specificity, and biocompatibility. The importance of connecting real challenges of materials and drugs with click–clip reactions research is highly anticipated, thereby contributing to precise and sustainable chemistry.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"112 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731799","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}
Covalent organic frameworks (COFs) have emerged as promising photocatalysts for H2O2 production due to their periodic and tunable structures. However, their photocatalytic performance is often limited by inefficient exciton dissociation and charge transport. Herein, three highly conjugated three-dimensional (3D) COFs with donor-acceptor (D-A) structures were synthesized to promote the photogenerated electron-hole separation and transport. To further enhance photocatalytic efficiency, electron-rich thiophene units were incorporated into the pore walls. Among the synthesized COFs, thiophene-modified COF-2 demonstrated an exceptional H2O2 generation rate of 10.68 mmol g-1 h-1 using 10% benzyl alcohol as a sacrificial agent, approximately 2.6 times higher than that of COF-1(4.12 mmol g-1 h-1) devoid of substituents. Interestingly, COF-3, featuring more extended conjugation through thianaphthene substituents, failed to achieve a higher H2O2 generation rate. Experimental characterizations confirmed that the superior performance of COF-2 originates from improved charge separation and transport, while theoretical analyses revealed that pore wall engineering significantly regulates the excited-state properties of 3D COFs. This work provides new insights into the molecular-level design of efficient 3D COF-based photocatalysts for sustainable H2O2 production.
{"title":"Pore Wall Engineering of Conjugated Three-Dimensional Covalent Organic Frameworks for Enhanced Hydrogen Peroxide Photosynthesis","authors":"Xin Zhao, Guoye Yu, Xuhan Zheng, Yuanping Yi, Guangchao Han, Yingjie Zhao, Yuancheng Wang","doi":"10.31635/ccschem.025.202506831","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506831","url":null,"abstract":"Covalent organic frameworks (COFs) have emerged as promising photocatalysts for H<sub>2</sub>O<sub>2</sub> production due to their periodic and tunable structures. However, their photocatalytic performance is often limited by inefficient exciton dissociation and charge transport. Herein, three highly conjugated three-dimensional (3D) COFs with donor-acceptor (D-A) structures were synthesized to promote the photogenerated electron-hole separation and transport. To further enhance photocatalytic efficiency, electron-rich thiophene units were incorporated into the pore walls. Among the synthesized COFs, thiophene-modified COF-2 demonstrated an exceptional H<sub>2</sub>O<sub>2</sub> generation rate of 10.68 mmol g<sup>-1</sup> h<sup>-1</sup> using 10% benzyl alcohol as a sacrificial agent, approximately 2.6 times higher than that of COF-1(4.12 mmol g<sup>-1</sup> h<sup>-1</sup>) devoid of substituents. Interestingly, COF-3, featuring more extended conjugation through thianaphthene substituents, failed to achieve a higher H<sub>2</sub>O<sub>2</sub> generation rate. Experimental characterizations confirmed that the superior performance of COF-2 originates from improved charge separation and transport, while theoretical analyses revealed that pore wall engineering significantly regulates the excited-state properties of 3D COFs. This work provides new insights into the molecular-level design of efficient 3D COF-based photocatalysts for sustainable H<sub>2</sub>O<sub>2</sub> production.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"20 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717425","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}
Helicoidal structures, inherently chiral when adopting a preferred-handed conformation, hold great promise for a variety of applications. However, the rational design and synthesis of helicoidal structures with controlled handedness at the molecular level remain formidable challenges, which further limit the comprehensive understanding of multiscale chirality transfer within such hierarchical systems. Herein, we incorporated (−)/(+)-pineno-fused 2,2′:6′,2″-terpyridine into polymer backbones, and constructed metallo-helicoids with preferred-handed conformations. Chiroptical studies and direct visualization of the screw-sense of metallo-helicoids elucidate the hierarchical chirality transfer, ranging from chiral center to coordination junction, helicoidal surface, entire helicoidal backbone, assembly of multiple helicoid chains, and ultimately extending to interactions with achiral guests. Moreover, super-helices as several strands of metallo-helicoid chains were reversibly formed by treating/removing water from the polymer solution, leading to an inverse screw-sense compared with individual metallo-helicoids. Such super-helices are further able to induce the chiroptical activity of achiral dye molecules via intermolecular electrostatic interactions, thereby resulting in a significant enhancement of circularly polarized luminescence. Our study not only enables precise control over the handedness of metallo-helicoids but also serves as an ideal platform for investigating chirality transfer across a wide range of length scales.
{"title":"Hierarchical Chirality Transfer and Reversible Chiroptical Switching in Metallo-Helicoids","authors":"Feng Su, Yinzhi Zhu, Runxu Tang, Shunran Zhang, Wenjing Zhang, Zhengong Meng, Weijia Wu, Yue Wu, Fang Fang, Zhi Chen, Haifeng Dong, Heng Wang, Xiujun Yu, Xiaopeng Li","doi":"10.31635/ccschem.025.202506664","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506664","url":null,"abstract":"Helicoidal structures, inherently chiral when adopting a preferred-handed conformation, hold great promise for a variety of applications. However, the rational design and synthesis of helicoidal structures with controlled handedness at the molecular level remain formidable challenges, which further limit the comprehensive understanding of multiscale chirality transfer within such hierarchical systems. Herein, we incorporated (−)/(+)-pineno-fused 2,2′:6′,2″-terpyridine into polymer backbones, and constructed metallo-helicoids with preferred-handed conformations. Chiroptical studies and direct visualization of the screw-sense of metallo-helicoids elucidate the hierarchical chirality transfer, ranging from chiral center to coordination junction, helicoidal surface, entire helicoidal backbone, assembly of multiple helicoid chains, and ultimately extending to interactions with achiral guests. Moreover, super-helices as several strands of metallo-helicoid chains were reversibly formed by treating/removing water from the polymer solution, leading to an inverse screw-sense compared with individual metallo-helicoids. Such super-helices are further able to induce the chiroptical activity of achiral dye molecules via intermolecular electrostatic interactions, thereby resulting in a significant enhancement of circularly polarized luminescence. Our study not only enables precise control over the handedness of metallo-helicoids but also serves as an ideal platform for investigating chirality transfer across a wide range of length scales.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"38 1","pages":"1-16"},"PeriodicalIF":11.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711592","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}
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