Chemical Science最新文献

{"title":"Extension of the π-conjugated core of methylchalcogenolated polycyclic aromatic hydrocarbon: synthesis and characterization of 1,4,7,10-tetrakis(methylthio)- and tetramethoxy-coronene","authors":"Prasanta Pal, Kirill Bulgarevich, Ryota Hanaki, Kohsuke Kawabata, Kazuo Takimiya","doi":"10.1039/d5sc03215f","DOIUrl":"https://doi.org/10.1039/d5sc03215f","url":null,"abstract":"Controlling the crystal structures of polycyclic aromatic hydrocarbons (PAHs) by regioselective methyl chalcogenolation is an effective strategy for realizing superior molecular semiconductors showing ultrahigh mobility, as exemplified by methylthiolated pyrene and peropyrene. Following the strategy, we designed and synthesized 1,4,7,10-tetrakis(methylthio)coronene (MT-coronene) and 1,4,7,10-tetramethoxycoronene (MO-coronene) as potential candidates for high-performance molecular semiconductors. Since the coronene core is highly symmetric, the regioselective functionalization at the 1,4,7,10-positions seemed to be challenging, and thus, we tested two strategies for constructing such regio-selectively functionalized coronene derivatives; one was the direct functionalization of parent coronene via the iridium-catalyzed borylation reaction, and the other was the stepwise construction of the coronene core with functionalized naphthalene derivatives. Interestingly, the former was suitable for the synthesis of MT-coronene, whereas the latter was suitable for MO-coronene. The crystal structures of MT- and MO-coronene were significantly different from the γ-structure of their parent and classified into the brickwork and the sandwich herringbone structure, respectively. In accordance with the brickwork crystal structures with isotropic but small intermolecular HOMO overlaps, the MT-coronene-based single-crystal field-effect transistors (SC-FETs) showed decent transistor responses with the carrier mobility of up to 0.5 cm<small>²</small> V<small>^–1</small>s<small>^–1</small>. On the other hand, the SC-FETs of MO-coronene, the solid-state electronic structure of which was zero-dimensional due to the sandwich herringbone structure, were far inferior to those of MT-coronene. Based on the crystal structures and theoretical calculations on MT- and MO-coronene, we analyzed the tendency of the intermolecular interactions and intermolecular HOMO overlaps in the solid state, which explains the performances of the coronene system as molecular semiconductors. Furthermore, we compared the solid-state structures of a series of methylthiolated PAHs, pyrene, perylene, peropyrene, and coronene, to figure out the differences in the performances as molecular semiconductors, which gave us new insights into the relationship between the molecular, packing, and electronic structure in the solid state, showing viewpoints for superior molecular semiconductors.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"25 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144670002","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":"Chemical and Mechanical Modifications of Flexible Metal–Organic Frameworks for Enhancing Photocatalysis","authors":"Yifan Liu, Huihui He, Lei Gao, Rong-Ran Liang, Ji Li, Jinyi Huang, Ya Yin, Yuxuan Meng, Yuxiu Zhong, Rengan Luo, Liangliang Zhang, Hong-Cai Zhou, Shuai Yuan","doi":"10.1039/d5sc02797g","DOIUrl":"https://doi.org/10.1039/d5sc02797g","url":null,"abstract":"Postsynthetic modification (PSM) has been widely employed to enhance the functionality of metal–organic frameworks (MOFs) for applications such as gas storage, light harvesting, and catalysis. However, the critical role of framework flexibility in enabling diverse modification pathways and influencing framework properties remains underexplored. In this work, we demonstrate that flexible MOFs offer unique advantages for PSM, using the flexible PCN-128 as a platform for both chemical and mechanical modifications to enhance photocatalytic CO2 reduction activity. Mechanical force induces piezochromic behavior, while sequential postsynthetic annulation reactions extend the π-conjugation of aromatic ligands within PCN-128, both modulating the energy band positions and enhancing visible light absorption. Single-crystal-to-single-crystal transformations were realized throughout the PSM process, offering valuable insights into the transformation process and structure-property relationships. Furthermore, metallo-phthalocyanine-based ligands (M-TcPC, M = Fe, Co, Ni) were introduced as catalytic sites for CO2 reduction via PSM strategies. By optimizing the ratio of photosensitizers to catalytic sites, the modified catalysts achieved a remarkable CO2 reduction rate of 838 μmol·g–1·h–1 under visible light irradiation. This study highlights the untapped potential of flexible MOFs in applying postsynthetic modification strategies to develop advanced photocatalysts for sustainable energy conversion.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144669977","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":"Entanglement of Spin Transition and Structural Adaptability: Manipulating the Slow Spin Equilibrium by Guest-Mediated Fine-Tuning Elastic Frustration","authors":"Yuqiao Chai, Yu-Ting Yang, Xue Jinpeng","doi":"10.1039/d5sc01202c","DOIUrl":"https://doi.org/10.1039/d5sc01202c","url":null,"abstract":"A comprehensive analysis of the physical and chemical properties using the same family of complexes is crucial for understanding and designing structure-property relationships. However, finding the appropriate system remains challenging. Here, a series of guest-saturated states based on the 2D Hofmann-type framework [FeII(prentrz)2PdII(CN)4]·guest (prentrz = (1E,2E)-3-phenyl-N-(4H-1,2,4-triazol-4-yl)prop-2-en-1-imine, 1·guest) is reported, which exhibit a guest-manipulated slow dynamic effect of spin equilibrium in an incomplete two-step spin-crossover (SCO) process. Using a full-sealed method by modulating the mixing ratios and types of CH3OH, H2O, and D2O, stable maintenance of guest-saturated states allows fine-tuning elastic frustration (ξ) of the framework to realize SCO behaviors in the unexplored region between one-step incomplete (HS0.5LS0.5↔HS) and two-step complete (LS↔HS0.5LS0.5↔HS) processes. A semi-sealed method enables continuous guest molecule loss until the guest-saturated state disappears, transitioning slow spin equilibrium from difficult to overcome to overcome fully. The study demonstrates that guest molecule modulation is more controllable than structural deformation effects on elastic frustration, offering a pathway to discover hidden types of SCO materials and develop new stimulus-responsive materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"102 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144669984","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":"Visible-Light Responsive Indoleazopyrazole Photoswitches: Dual-Enhancement of Redshift and Half-life by Ester Modification at the Ortho Position","authors":"Xuanchi Yu, Chenyu Zhang, Dongfang Dong, Bing Liu, Dali Wang, Tao Li","doi":"10.1039/d5sc03275j","DOIUrl":"https://doi.org/10.1039/d5sc03275j","url":null,"abstract":"As a class of universal light-responsive units, most azo compounds require ultraviolet (UV) excitation. Most conventional π→π* redshift strategies, while enabling visible-light excitation, often compromise the thermal stability of the Z-isomer. Herein, we designed a series of ortho-substituted indoleazopyrazoles that simultaneously achieve visible-light responsiveness and exceptional thermal stability. Notably, ester substitution at the ortho-position (relative to the azo group) of the indoleazopyrazole exhibits a λmax (π→π*) redshift to 383 nm while maintaining a half-life of up to 4.7 days. Following water-soluble modification, the optimized ester substitution derivative 5-photosurfactant (5-PS) demonstrates visible-light-controlled bioactivity, switching between low toxicity (E-isomer) and high toxicity (Z-isomer) in three human cancer cell lines. Remarkably, the half–maximal inhibitory concentrations (IC50) of E-isomer is approximately three-fold higher than that of the Z-rich isomer in HepG2 cells. This strategy achieves the dual enhancement of π→π* redshift and half-life, opening a new avenue for visible-light-controlled targeted anticancer therapy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144669979","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":"High-Entropy Alloy Catalysts with Tunable Electronic Configurations for Enhanced Sulfur Reduction Electrocatalysis","authors":"Jingge Shi, Xu He, Hao Zhang, Wei Jiang, Ruizheng Zhao, Mamman Wu, Yongzheng Fang, Menggai Jiao, Yiyang Liu, Zhen Zhou","doi":"10.1039/d5sc04586j","DOIUrl":"https://doi.org/10.1039/d5sc04586j","url":null,"abstract":"The shuttle effect and sluggish redox kinetics of polysulfides pose significant challenges to the long-cycle stability of alkali metal-sulfur batteries, necessitating the development of highly efficient catalysts. High-entropy alloys (HEAs) have emerged as promising electrocatalysts for energy storage due to their unique electronic properties and high configurational entropy. Tailoring the electronic configuration of HEAs to achieve a well-positioned d-band center is a vital strategy for enhancing catalytic performance in alkali metal-sulfur batteries systems. In this study, the electronic configurations of HEAs were systematically tuned by varying the fifth metal element. Among them, NiCoFeCuMo (HEA-Mo) exhibited an optimized electronic configuration and a favorable d-band center, fully demonstrating the “cocktail effect” and thereby enhancing interactions with polysulfides. To evaluate its practical performance, HEA-Mo was integrated into polypropylene (PP) separators (HEA-Mo@PP) for Li-S and room-temperature Na-S batteries, both exhibiting excellent cyclic stability attributed to enhanced polysulfides adsorption and catalytic conversion. This work provides critical insight into the rational design of non-noble HEAs via electronic configuration modulation, offering a generalizable strategy for advancing next-generation energy storage systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"97 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144670003","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":"Polythiophenes as electron donors in organic solar cells","authors":"Xiyue Yuan, Jianglong Li, Wanting Deng, Xia Zhou, Chunhui Duan","doi":"10.1039/d5sc03154k","DOIUrl":"https://doi.org/10.1039/d5sc03154k","url":null,"abstract":"Recent advancements in organic solar cells (OSCs) highlight the critical need for low-cost, readily available polymer donors to facilitate the commercialization of OSCs. Among the various photovoltaic materials, polythiophene (PT) and its derivatives have emerged as the most promising candidates for commercial applications, primarily due to their affordability and ease of scalable synthesis. Over the past few years, the combination of PTs with nonfullerene acceptors (NFAs) has led to significant improvements in photovoltaic efficiency. This paper provides a comprehensive overview of design strategies for polythiophene electron donors utilized in NFA-based OSCs, focusing on the modulation of energy levels and aggregation properties. It also evaluates recent progress in optimizing film morphology in PT:NFA blends, emphasizing key factors like donor-acceptor miscibility, solution-state aggregation control, and film-formation kinetics. Additionally, the paper explores the applications of PTs in all-polymer OSCs and large-area OSCs, as well as the stability of PT-based OSCs. Finally, the paper addresses scientific challenges associated with PT-based OSCs, aiming to provide guidance and stimulate new ideas for further research.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677783","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":"Planarisation or a twist? Using steric engineering to unlock the origin of mechanofluorochromic red-shifts","authors":"Peter William McDonald, Lars Goerigk, Chris Ritchie","doi":"10.1039/d5sc04257g","DOIUrl":"https://doi.org/10.1039/d5sc04257g","url":null,"abstract":"Engineering the ground-state orientations of donor and acceptor groups through steric control of fluorophore conformations is an effective strategy for manipulating molecular electronics and, in turn, their emissive properties. Where strong emission is retained in the crystalline state, a correlation of structure with photophysical properties can be made, as is the case for the five pyridinium betaines reported herein. Our findings provide strong evidence that an increase in dihedral angle between N,N-diphenylamino donor and/or pyridinium acceptor induces a notable red-shift in emission maximum, with the mechanofluorochromic response also correlated with the same process. This research aims to address the oft-invoked explanation that planarisation induces red-shifted emission, highlighting that this effect is not universal and that systematic studies are essential. Further, this elegant steric engineering approach may be applied to other mechanochromic systems to determine the nature of their geometry changes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"187 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144669986","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":"Molecular engineering of porphyrin dyes and copper complexes for enhanced dye regeneration toward high-performance dye-sensitized solar cells using copper(I/II) redox shuttles","authors":"Yuzhe Zhang, Tomohiro Higashino, Keigo Namikawa, W. Ryan Osterloh, Hiroshi Imahori","doi":"10.1039/d5sc03537f","DOIUrl":"https://doi.org/10.1039/d5sc03537f","url":null,"abstract":"Porphyrin dyes have garnered significant attention as promising photosensitizers for dye-sensitized solar cells (DSSCs) due to their exceptional light-harvesting capabilities and remarkable power conversion efficiencies (PCEs) when paired with cobalt(<small>II</small>/<small>III</small>) complex-based redox shuttles. Meanwhile, copper(<small>I</small>/<small>II</small>) complexes have emerged as new generation redox shuttles, achieving impressive open-circuit voltages (<em>V</em><small>_OC</small>) exceeding 1.0 V. However, porphyrin-based DSSCs using copper(<small>I</small>/<small>II</small>) redox shuttles have struggled with low-to-moderate PCEs, primarily due to insufficient driving forces for the dye regeneration process. In this study, we introduce <strong>FL1</strong>, a novel porphyrin dye featuring a fluorene moiety with reduced electron-donating properties, designed to ensure a sufficient driving force for dye regeneration using copper(<small>I</small>/<small>II</small>) complexes. Under optimized conditions, DSSC incorporating <strong>FL1</strong> with a copper(<small>I</small>/<small>II</small>) complex utilizing 4,4′-dimethoxy-6,6′-dimethyl-2,2′-bipyridine <strong>[Cu(2MeOby)<small>₂</small>][TFSI]</strong>/<strong>[Cu(2MeOby)<small>₂</small>][TFSI]<small>₂</small></strong> achieved a notable PCE of 8.30% with a <em>V</em><small>_OC</small> of 0.890 V. Furthermore, our investigation into counterion effects revealed that DSSCs employing <strong>[Cu(2MeOby)<small>₂</small>][PF<small>₆</small>]</strong>/<strong>[Cu(2MeOby)<small>₂</small>][PF<small>₆</small>]<small>₂</small></strong> as a redox shuttle delivered the highest PCE of 9.06% with a <em>V</em><small>_OC</small> of 0.900 V, attributed to its superior diffusion coefficient. Finally, co-sensitized DSSCs featuring <strong>FL1</strong> and <strong>XY1B</strong> achieved an outstanding PCE of 10.9%, while retaining a high <em>V</em><small>_OC</small> of 0.945 V, setting a new benchmark efficiency for porphyrin-based DSSCs utilizing copper(<small>I</small>/<small>II</small>) redox shuttles. This breakthrough highlights the immense potential of further refining porphyrin dyes and copper(<small>I</small>/<small>II</small>) redox shuttles through energy-level engineering to optimize the driving force for dye regeneration and propel advancements in DSSC technology.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"25 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144669997","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":"Modulating the Direction of Catalytic Glyoximate Sites of Covalent Organic Frameworks towards Electrocatalytic Nitrate Reduction","authors":"Shuai Yang, Shuai Bi, Lipeng Zhai, Qing Xu","doi":"10.1039/d5sc02151k","DOIUrl":"https://doi.org/10.1039/d5sc02151k","url":null,"abstract":"Two-dimensional (2D) covalent organic frameworks (COFs) with metal centers are ideal template to construct electrrocatalysts due to their high degree of structural controllability. However, the metal centers were stacked in column with limited space, which impeded mass delivered to catalytic sites across the pore channels. Herein, we have first demonstrated topologic synthesis strategy to construct catalytic sites in three-dimensional (3D) direction. The designed 3D COF adopted ffc topology, with large space of 1.15 and 1.53 nm between the metal sites along parallel and vertical directions, respectively. The in-situ spectroscopies revealed 100% Ni-N4 sites in 3D frameworks have reconstructed to Ni N4-NO, while the reconstruction proportion of Ni-N4 sites was 40% for 2D COF (with a distance between metal sites of 0.38 nm). The catalytic 3D COF enable to electrochemical synthesize of NH3 via reduction of nitrate (NO3RR) with a rate of 9.51 mg mgcat−1 h−1, 140% of that from the 2D catalytic at −0.7 V vs RHE. The theoretical calculation further revealed the reconstructed Ni N4-NO site had a stronger binding ability of the reactants and intermediates than that of the initial Ni-N4 site, and thus contributed to higher activity. This work provides general design strategies for heterogeneous catalysts in electrocatalytic systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"118 Suppl 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144669999","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":"Confined Growth of UiO-66 into Ultrahigh-loading Membrane for Efficient Hexane Isomer Separation","authors":"Pan-Pan Zhang, Jing-Ran Yu, Jiayu Ding, Wei-Hai Lin, Zhen Chen, Wei Shao, Shuchang Wang, Yi-Le Chen, Yi Li, Qihan Gong, Ming Xue, Xiao-Ming Chen","doi":"10.1039/d5sc04212g","DOIUrl":"https://doi.org/10.1039/d5sc04212g","url":null,"abstract":"The efficient separation of hexane isomers is a crucial process for the petrochemical industry. Mixed-matrix membranes (MMMs) hold tremendous potential for hexane isomer separation. However, maintaining their continuity at high filler loading remains a substantial challenge. Here, UiO-66/PP mixed-matrix membranes are fabricated via in situ confined growth synthesis strategy that achieves an exceptional filler loading of 72.9 wt%. The resulting UiO-66/PP-(96) membrane maintains structural continuity while effectively discriminating linear and mono-branched hexane isomers from their di-branched counterparts, exhibiting a flux of 473.5 g·m⁻²·h⁻¹ and separation factor of 4.53 for n-hexane/2,2-dimethylbutane mixtures. Remarkably, this membrane enriches n-hexane content from 50.0 wt% in the feed to 81.9 wt% in the permeate through a single processing stage, while maintaining robust performance across various hexane isomer combinations. These characteristics highlight its potential for extracting linear alkanes to enhance gasoline research octane number (RON). Molecular dynamics (MD) simulations corroborate these findings, revealing faster transport kinetics for n-hexane compared to branched isomers. This straightforward synthesis approach presented herein significantly broadens the avenues for the advancement of MOF mixed-matrix membranes in petrochemical separation applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144664412","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}