Bo Peng, Ming-Qing Chen, Tengfei Ma, Yi-Fan Huang, Peng Wang, Weimin Liu
Carotenoids extend the absorption range of photosynthesis and transfer excitation energy to (Bacterio-)chlorophylls with remarkable efficiency, yet the microscopic mechanism of this process, especially the role of the SX intermediate remains unresolved. Here, we use femtosecond stimulated Raman spectroscopy, whose high vibrational frequency and temporal resolutions enable direct tracking of excited-state intermediates and their symmetry characteristics. By probing spheroidene in both solution and light-harvesting 2 complex of Rhodobacter sphaeroides, we reveal structural change in S2 (1Bu+) state that form distorted SX and S1 (2Ag−) intermediates. The SX state is assigned to optically forbidden 3Ag− configuration rather than the earlier 1Bu− or Ag+ proposals, and is identified as an efficient pathway for energy transfer to bacteriochlorophylls. The spheroidene-to-bacteriochlorophyll energy transfer efficiencies are quantified as 32% via SX state, combine with 50% from the S2 state and 12% from the S1 state, yielding an overall transfer efficiency of 94%, in excellent agreement with previous reports. We propose that the observed structural distortions of spheroidene dynamically enhance Coulombic coupling with surrounding bacteriochlorophylls, which may underlie the remarkably high efficiency of excitation energy transfer.
{"title":"Dynamic-Structural-Distortion of Spheroidene Activates a Hidden 3Ag− State Mediating Carotenoid-to-Bacteriochlorophyll Energy Transfer in Light-harvesting 2","authors":"Bo Peng, Ming-Qing Chen, Tengfei Ma, Yi-Fan Huang, Peng Wang, Weimin Liu","doi":"10.1039/d5sc08508j","DOIUrl":"https://doi.org/10.1039/d5sc08508j","url":null,"abstract":"Carotenoids extend the absorption range of photosynthesis and transfer excitation energy to (Bacterio-)chlorophylls with remarkable efficiency, yet the microscopic mechanism of this process, especially the role of the S<small><sub>X</sub></small> intermediate remains unresolved. Here, we use femtosecond stimulated Raman spectroscopy, whose high vibrational frequency and temporal resolutions enable direct tracking of excited-state intermediates and their symmetry characteristics. By probing spheroidene in both solution and light-harvesting 2 complex of Rhodobacter sphaeroides, we reveal structural change in S<small><sub>2</sub></small> (1B<small><sub>u</sub></small><small><sup>+</sup></small>) state that form distorted S<small><sub>X</sub></small> and S<small><sub>1</sub></small> (2A<small><sub>g</sub></small><small><sup>−</sup></small>) intermediates. The S<small><sub>X</sub></small> state is assigned to optically forbidden 3A<small><sub>g</sub></small><small><sup>−</sup></small> configuration rather than the earlier 1B<small><sub>u</sub></small><small><sup>−</sup></small> or A<small><sub>g</sub></small><small><sup>+</sup></small> proposals, and is identified as an efficient pathway for energy transfer to bacteriochlorophylls. The spheroidene-to-bacteriochlorophyll energy transfer efficiencies are quantified as 32% via S<small><sub>X</sub></small> state, combine with 50% from the S2 state and 12% from the S<small><sub>1</sub></small> state, yielding an overall transfer efficiency of 94%, in excellent agreement with previous reports. We propose that the observed structural distortions of spheroidene dynamically enhance Coulombic coupling with surrounding bacteriochlorophylls, which may underlie the remarkably high efficiency of excitation energy transfer.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116044","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}
Linchangqing Yang, Yijing Zong, Meng Yin, Wencai Yi, Jungfang Li, Jie Lin, Qinghong Kong, Guangcheng Xi
The formation of transition metal nitrides (TMNs) necessitates overcoming extremely high reaction barriers, which renders the precise synthesis of TMN materials with tailored structures a significant challenge. Herein, we propose a molten-salt/template strategy for the accurate customization of TMNs featuring a rare single-crystal ordered mesoporous (SCOM) structure. By leveraging this strategy, 5 types of SCOM-structured TMNs—including WN, MoN, TiN, VN, and CoN were synthesized. Hydroxylation of templates and the subsequent formation of SCOM-structured metal oxides were identified as the key factors governing the formation of SCOM-TMNs. Interestingly, these SCOM-structured WN lack the intrinsic Raman signals typically possessed by non-metallic materials, effectively resolving the long-standing issue of background interference in non-metallic surface-enhanced Raman scattering (SERS) substrates. The WN substrate achieves an ultrahigh Raman enhancement factor of up to 7.5×10⁷ and an ultralow detection limit of 1×10⁻¹² M.
{"title":"Single-Crystal-Ordered-Mesoporous Metal Nitrides without Intrinsic Raman Signals for Highly Sensitive SERS Detection","authors":"Linchangqing Yang, Yijing Zong, Meng Yin, Wencai Yi, Jungfang Li, Jie Lin, Qinghong Kong, Guangcheng Xi","doi":"10.1039/d5sc09344a","DOIUrl":"https://doi.org/10.1039/d5sc09344a","url":null,"abstract":"The formation of transition metal nitrides (TMNs) necessitates overcoming extremely high reaction barriers, which renders the precise synthesis of TMN materials with tailored structures a significant challenge. Herein, we propose a molten-salt/template strategy for the accurate customization of TMNs featuring a rare single-crystal ordered mesoporous (SCOM) structure. By leveraging this strategy, 5 types of SCOM-structured TMNs—including WN, MoN, TiN, VN, and CoN were synthesized. Hydroxylation of templates and the subsequent formation of SCOM-structured metal oxides were identified as the key factors governing the formation of SCOM-TMNs. Interestingly, these SCOM-structured WN lack the intrinsic Raman signals typically possessed by non-metallic materials, effectively resolving the long-standing issue of background interference in non-metallic surface-enhanced Raman scattering (SERS) substrates. The WN substrate achieves an ultrahigh Raman enhancement factor of up to 7.5×10⁷ and an ultralow detection limit of 1×10⁻¹² M.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"46 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116094","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}
Metal–organic frameworks (MOFs) feature a rich structural diversity, including crystalline, amorphous, and liquid phases of varying topologies. Their structural characterization is often performed either at the local scale (through pair distribution functions, bond angle distributions, etc.) or, for crystalline phases, through topology analysis of the periodic framework — leaving out disordered and amorphous phases. In this work, we develop a computational methodology for the structural characterization of middle-range order in MOFs that is applicable to both crystalline and amorphous phases. We base our method on the statistical analysis of the geometry of the supramolecular framework at the microscopic level, and its evolution during molecular simulation. We analyze the statistics of metal–organic rings, their distribution in size, as well as their geometrical characteristics through mathematical tools derived from polymer physics: radius of gyration, asphericity, and writhe. We show that this advanced characterization can be leveraged for the identification of phases and the detection and analysis of phase transitions.
{"title":"Identifying Phase Transitions in Zeolitic Imidazolate Frameworks: Microscopic Insight from Molecular Simulations","authors":"Léna Triestram, François-Xavier Coudert","doi":"10.1039/d5sc09468b","DOIUrl":"https://doi.org/10.1039/d5sc09468b","url":null,"abstract":"Metal–organic frameworks (MOFs) feature a rich structural diversity, including crystalline, amorphous, and liquid phases of varying topologies. Their structural characterization is often performed either at the local scale (through pair distribution functions, bond angle distributions, etc.) or, for crystalline phases, through topology analysis of the periodic framework — leaving out disordered and amorphous phases. In this work, we develop a computational methodology for the structural characterization of middle-range order in MOFs that is applicable to both crystalline and amorphous phases. We base our method on the statistical analysis of the geometry of the supramolecular framework at the microscopic level, and its evolution during molecular simulation. We analyze the statistics of metal–organic rings, their distribution in size, as well as their geometrical characteristics through mathematical tools derived from polymer physics: radius of gyration, asphericity, and writhe. We show that this advanced characterization can be leveraged for the identification of phases and the detection and analysis of phase transitions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116115","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}
Reversed C-acyl glycosides represent a versatile class of nonclassical glycosides with potential in complex carbohydrate synthesis, including L-sugars, higher-carbon sugars, and medicinal chemistry. Conventional strategies for L- and higher-carbon sugars are limited by multi-step protection–deprotection sequences and poor stereocontrol. Herein, we report a general Pd-catalyzed reversed acyl C-glycosylation that efficiently couples configurationally stable reversed glycosyl stannanes with C(sp²)- and C(sp³)-derived thioesters under mild conditions. The reaction proceeds with complete stereoretentive transfer, enabling precise access to both D- and L-type glycosides, including higher-carbon sugar derivatives and C-ferrocenecarbonyl glycosides. The broad substrate scope, excellent functional group tolerance, and predictable stereochemical outcome highlight the robustness and synthetic versatility of this approach. Applications of the resulting reversed C-acyl glycosides as chiral synthons enable D-to-L interconversion, construction of L-sugar analogues, and derivatization toward designer carbohydrate frameworks. Importantly, this transformation enables a distinct D-to-L conversion featuring simultaneous C4 and C5 inversion, unlike conventional methods that modify only C5 configuration. Overall, this protocol establishes a general platform for stereocontrolled construction and diversification of structurally defined nonclassical glycosides, providing a foundation for glycodiversification, complex sugar synthesis, and exploration of biologically relevant C-glycosyl scaffolds.
{"title":"Pd-Catalyzed Stereospecific Synthesis of Reversed C-Acyl Glycosides: Access to Rare L-Sugars and Higher-Carbon Sugars","authors":"Guoqiang Cheng, Bo Yang, Feng Zhu","doi":"10.1039/d5sc08224b","DOIUrl":"https://doi.org/10.1039/d5sc08224b","url":null,"abstract":"Reversed C-acyl glycosides represent a versatile class of nonclassical glycosides with potential in complex carbohydrate synthesis, including L-sugars, higher-carbon sugars, and medicinal chemistry. Conventional strategies for L- and higher-carbon sugars are limited by multi-step protection–deprotection sequences and poor stereocontrol. Herein, we report a general Pd-catalyzed reversed acyl C-glycosylation that efficiently couples configurationally stable reversed glycosyl stannanes with C(sp²)- and C(sp³)-derived thioesters under mild conditions. The reaction proceeds with complete stereoretentive transfer, enabling precise access to both D- and L-type glycosides, including higher-carbon sugar derivatives and C-ferrocenecarbonyl glycosides. The broad substrate scope, excellent functional group tolerance, and predictable stereochemical outcome highlight the robustness and synthetic versatility of this approach. Applications of the resulting reversed C-acyl glycosides as chiral synthons enable D-to-L interconversion, construction of L-sugar analogues, and derivatization toward designer carbohydrate frameworks. Importantly, this transformation enables a distinct D-to-L conversion featuring simultaneous C4 and C5 inversion, unlike conventional methods that modify only C5 configuration. Overall, this protocol establishes a general platform for stereocontrolled construction and diversification of structurally defined nonclassical glycosides, providing a foundation for glycodiversification, complex sugar synthesis, and exploration of biologically relevant C-glycosyl scaffolds.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098309","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}
Kang Guo, Yaokang Lv, Ziyang Song, Lihua Gan, Mingxian Liu
Rechargeable aqueous zinc-ion batteries (AZIBs) have attracted great attention due to their inherent advantages such as high safety, low cost, and environmental friendliness, making them one of the most promising alternatives to traditional lithium-ion batteries. The rational design and continuous optimization of versatile inorganic cathode materials play a crucial role in achieving practical applications. In this review, we first systematically classify inorganic cathode materials and their design strategies, including manganese oxides with rich redox chemistry, vanadium compounds with multiple oxidation states, Prussian blue analogues with open skeleton channels, layered transition metal disulfides with unique interlayer ion storage capabilities, and halogens with reversible multielectron capacity. Furthermore, the structural characteristics, electrochemical performances, and crucial improvement methods of these cathode materials are discussed in detail. Finally, we outline the challenges and the prospects of inorganic cathodes in AZIBs to guide the future development of next-generation energy communities.
{"title":"Positioning versatile inorganic cathode materials in the aqueous zinc-ion battery landscape.","authors":"Kang Guo, Yaokang Lv, Ziyang Song, Lihua Gan, Mingxian Liu","doi":"10.1039/d5sc09531j","DOIUrl":"https://doi.org/10.1039/d5sc09531j","url":null,"abstract":"<p><p>Rechargeable aqueous zinc-ion batteries (AZIBs) have attracted great attention due to their inherent advantages such as high safety, low cost, and environmental friendliness, making them one of the most promising alternatives to traditional lithium-ion batteries. The rational design and continuous optimization of versatile inorganic cathode materials play a crucial role in achieving practical applications. In this review, we first systematically classify inorganic cathode materials and their design strategies, including manganese oxides with rich redox chemistry, vanadium compounds with multiple oxidation states, Prussian blue analogues with open skeleton channels, layered transition metal disulfides with unique interlayer ion storage capabilities, and halogens with reversible multielectron capacity. Furthermore, the structural characteristics, electrochemical performances, and crucial improvement methods of these cathode materials are discussed in detail. Finally, we outline the challenges and the prospects of inorganic cathodes in AZIBs to guide the future development of next-generation energy communities.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12874711/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146141181","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electron-transfer (ET) and proton-transfer (PT) events occurring at electrochemical interfaces ultimately dictate the efficiency of electrocatalytic energy conversion and chemical synthesis. Despite their significance, a unified theoretical description of ET/PT dynamics has been challenging due to the entangled electronic, nuclear, and solvent degrees of freedom. Herein, we present a quantum-classical multiscale framework integrating constrained density functional theory (CDFT) with machine learning accelerated molecular dynamics (MLMD) to investigate ET and PT during electrochemical CO2 reduction on Cu(100) in explicit water. Distinct ML potentials are trained for the adiabatic ground state and for two charge-localized diabatic states, enabling efficient configurational sampling while preserving quantum-mechanical fidelity in electronic energies and forces. The derived diabatic free energy surfaces reveal that CO2 first undergoes inner-sphere ET to yield chemisorbed CO2-, followed by PT to form*COOH. Solvent reorganization imposes kinetic constraints on the ET step yet counterintuitively stabilizes the *CO2- intermediate through ion-dipole interactions, modulating the vibronic couplings. For PT, solvent relaxation dynamically adjusts the equilibrium donor-acceptor distance, thereby augmenting the Franck-Condon overlap between reactant and product vibronic wavefunctions in excited proton vibrational states, which facilitates nonadiabatic transitions across diabatic surfaces. Rate constants extracted by combining diabatic vibronic PCET theory with generalized Langevin equation-derived Grote-Hynes theory show that the sequential ET-PT pathway outpaces concerted PCET by about 5 orders of magnitude. This methodology establishes a robust paradigm for dissecting ET and PT kinetics at electrochemical interfaces, emphasizing the interplay of quantum nuclear effects, vibronic coupling, and solvent fluctuations.
{"title":"Resolving Sequential Electron-Proton Transfer Kinetics for Electrochemical CO2 Reduction at Cu(100)/H2O interface via a Quantum-Classical Framework","authors":"Yun Yang, Gang Fu","doi":"10.1039/d5sc07385e","DOIUrl":"https://doi.org/10.1039/d5sc07385e","url":null,"abstract":"Electron-transfer (ET) and proton-transfer (PT) events occurring at electrochemical interfaces ultimately dictate the efficiency of electrocatalytic energy conversion and chemical synthesis. Despite their significance, a unified theoretical description of ET/PT dynamics has been challenging due to the entangled electronic, nuclear, and solvent degrees of freedom. Herein, we present a quantum-classical multiscale framework integrating constrained density functional theory (CDFT) with machine learning accelerated molecular dynamics (MLMD) to investigate ET and PT during electrochemical CO<small><sub>2</sub></small> reduction on Cu(100) in explicit water. Distinct ML potentials are trained for the adiabatic ground state and for two charge-localized diabatic states, enabling efficient configurational sampling while preserving quantum-mechanical fidelity in electronic energies and forces. The derived diabatic free energy surfaces reveal that CO<small><sub>2</sub></small> first undergoes inner-sphere ET to yield chemisorbed <em>CO<small><sub>2</sub></small><small><sup>-</sup></small>, </em>followed by PT to form*COOH. Solvent reorganization imposes kinetic constraints on the ET step yet counterintuitively stabilizes the *CO<small><sub>2</sub></small><small><sup>-</sup></small> intermediate through ion-dipole interactions, modulating the vibronic couplings. For PT, solvent relaxation dynamically adjusts the equilibrium donor-acceptor distance, thereby augmenting the Franck-Condon overlap between reactant and product vibronic wavefunctions in excited proton vibrational states, which facilitates nonadiabatic transitions across diabatic surfaces. Rate constants extracted by combining diabatic vibronic PCET theory with generalized Langevin equation-derived Grote-Hynes theory show that the sequential ET-PT pathway outpaces concerted PCET by about 5 orders of magnitude. This methodology establishes a robust paradigm for dissecting ET and PT kinetics at electrochemical interfaces, emphasizing the interplay of quantum nuclear effects, vibronic coupling, and solvent fluctuations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098278","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}
Near-infrared (NIR) thermally activated delayed fluorescence (TADF) materials with emission peaks beyond 800 nm have attracted considerable attention owing to their potential applications in bioimaging, optical communication, and night-vision technologies. However, their development remains limited by the energy gap law, which leads to severe non-radiative decay and low external quantum efficiencies. In recent years, researchers have broken through these bottlenecks by employing various molecular design strategies, such as modulating charge-transfer characteristics and reducing the singlet–triplet energy splitting. These efforts have enabled the realization of efficient TADF emission extending into the deep NIR region. In this review, we summarize recent advances in NIR TADF emitters with emission maxima beyond 800 nm, focusing on their molecular design principles, photophysical properties, and device performance, and discuss future perspectives for achieving high-efficiency deep-NIR OLEDs.
{"title":"Beyond 800 nm: Recent Progress in High-Performance Near-Infrared Thermally Activated Delayed Fluorescence Based OLEDs","authors":"Shuo Li, Xiangyu Zhou, Lingjie Xu, Chao Yu, Junteng Liu, Shouke Yan, Zhongjie Ren","doi":"10.1039/d5sc09087c","DOIUrl":"https://doi.org/10.1039/d5sc09087c","url":null,"abstract":"Near-infrared (NIR) thermally activated delayed fluorescence (TADF) materials with emission peaks beyond 800 nm have attracted considerable attention owing to their potential applications in bioimaging, optical communication, and night-vision technologies. However, their development remains limited by the energy gap law, which leads to severe non-radiative decay and low external quantum efficiencies. In recent years, researchers have broken through these bottlenecks by employing various molecular design strategies, such as modulating charge-transfer characteristics and reducing the singlet–triplet energy splitting. These efforts have enabled the realization of efficient TADF emission extending into the deep NIR region. In this review, we summarize recent advances in NIR TADF emitters with emission maxima beyond 800 nm, focusing on their molecular design principles, photophysical properties, and device performance, and discuss future perspectives for achieving high-efficiency deep-NIR OLEDs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098280","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}
Sandra Díaz, Adrian Sanchez-Fernandez, Juan R Granja, Ignacio Insua, Javier Montenegro
The hierarchical self-assembly of three-dimensional (3D) supramolecular materials presents a significant challenge in molecular design. This process requires monomers with specific packing geometries and orthogonal contacts to enable multidimensional elongation. Here, we describe a new cyclic peptide design that allows hierarchical self-assemblyin all three spatial dimensions to produce nanosheets composed of ordered nanotube layers. The uniformity of the nanosheet aspect ratio and thickness is consistent with the high packing order of the monomers observed in this 3D assembly.
{"title":"3D self-assembly of cyclic peptides into multilayered nanosheets","authors":"Sandra Díaz, Adrian Sanchez-Fernandez, Juan R Granja, Ignacio Insua, Javier Montenegro","doi":"10.1039/d5sc09489e","DOIUrl":"https://doi.org/10.1039/d5sc09489e","url":null,"abstract":"The hierarchical self-assembly of three-dimensional (3D) supramolecular materials presents a significant challenge in molecular design. This process requires monomers with specific packing geometries and orthogonal contacts to enable multidimensional elongation. Here, we describe a new cyclic peptide design that allows hierarchical self-assemblyin all three spatial dimensions to produce nanosheets composed of ordered nanotube layers. The uniformity of the nanosheet aspect ratio and thickness is consistent with the high packing order of the monomers observed in this 3D assembly.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"253 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098282","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}
Bulky N-heterocyclic carbenes (NHCs) are powerful tools for controlling the coordination environment and reactivity at inorganic elements. Herein, we report an exceptionally bulky NHC, BnITr (BnITr = [(C6H4){NCPh3}2C:]), which features a percent buried volume (%Vbur) that exceeds 60%. The steric and electronic properties of BnITr were elucidated through a combined experimental and computational study focused on selected silver, gold, and rhodium complexes. The structural impact of the benzylated backbone in BnITr leads to the positioning of phenyl rings within the flanking N-trityl (CPh3, Tr) groups in close proximity to the carbene donor center, enabling the isolation/stabilization of hitherto elusive examples of (quasi)-monocoordinated lithium and gallium(I) cations. Attempts to generate the one-coordinate Pd(0) complex, [BnITr−Pd], led to an unusual redox-triggered ligand activation/−CPh3 group migration to palladium.
{"title":"Achieving (quasi)-monocoordination in metal complexes with an exceptionally bulky carbene ligand","authors":"Ludwig Zapf, Eric Rivard","doi":"10.1039/d5sc09514j","DOIUrl":"https://doi.org/10.1039/d5sc09514j","url":null,"abstract":"Bulky <em>N</em>-heterocyclic carbenes (NHCs) are powerful tools for controlling the coordination environment and reactivity at inorganic elements. Herein, we report an exceptionally bulky NHC, <small><sup>Bn</sup></small>ITr (<small><sup>Bn</sup></small>ITr = [(C<small><sub>6</sub></small>H<small><sub>4</sub></small>){NCPh<small><sub>3</sub></small>}<small><sub>2</sub></small>C:]), which features a percent buried volume (%<em>V</em><small><sub>bur</sub></small>) that exceeds 60%. The steric and electronic properties of <small><sup>Bn</sup></small>ITr were elucidated through a combined experimental and computational study focused on selected silver, gold, and rhodium complexes. The structural impact of the benzylated backbone in <small><sup>Bn</sup></small>ITr leads to the positioning of phenyl rings within the flanking <em>N</em>-trityl (CPh<small><sub>3</sub></small>, Tr) groups in close proximity to the carbene donor center, enabling the isolation/stabilization of hitherto elusive examples of (quasi)-monocoordinated lithium and gallium(I) cations. Attempts to generate the one-coordinate Pd(0) complex, [<small><sup>Bn</sup></small>ITr−Pd], led to an unusual redox-triggered ligand activation/−CPh<small><sub>3</sub></small> group migration to palladium.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116046","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}
Kais Dhbaibi, Thi-Huong Le, Jérome Marrot, Masahiro Hayakawa, Masashi Mamada, Michel Frigoli
Recent studies on acenes have highlighted a localized representation (LR) of the aromatic sextets, challenging Clar’s classical model of migrating sextets. Here we extend this framework to peri-fused systems by investigating bis(tri-isopropylsilyl)ethynyl (TIPS)-functionnalized polycyclic aromatic hydrocarbons (TIPS-PAHs) namely TIPS anthanthrene (TIPS-ATT), TIPS pyranthrene (TIPS-PYR) and TIPS dibenzo[pyranthrene] (TIPS-DBPYR) as test beds for LR. Crystal structures provide direct evidence for determining the Fries canonical structures, with bond lengths and bond length alternation (BLA) at the zig zag edge offering robust criteria for positioning aromatic sextets. While NICS and HOMA indices are broadly consistent with these assignments, their interpretation should be considered with some caution. Optical studies reveal progressive bathochromic shifts (491–599 nm) with increasing conjugation, but absorption strength and fluorescence quantum yield depend critically on the mode of π extension: catacondensation enhances brightness, whereas linear extension diminishes it. Remarkably, TIPS-PYR combines a record molar absorption coefficient (>200,000 M⁻¹·cm⁻¹) with high fluorescence quantum yield (ΦF = 0.93), yielding a molar brightness comparable to giant nanoribbons. Stability assays show that TIPS-ATT and TIPS-PYR are bench stable, whereas TIPS-DBPYR, despite reduced fluorescence efficiency, exhibits enhanced photostability relative to TIPS pentacene (TIPS-PEN) and satisfies the energetic criterion for singlet fission. These findings establish LR as a robust framework for describing peri fused PAHs, identify TIPS-PYR as an exceptionally bright dye, and position TIPS-DBPYR as a promising singlet fission material.
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