Chemical Science最新文献

{"title":"The underlying synergistic mechanism of co-solvents to fabricate high-quality FAPbI3 perovskite films","authors":"Zezhuan Jiang, Xiaofeng He, Cunyun Xu, Xiaoyun Wan, Haimao Zhu, Jiancheng You, Zhongjun Dai, Wenqi Zeng, Ping Li, Jin Ye, Qunliang Song","doi":"10.1039/d6sc00647g","DOIUrl":"https://doi.org/10.1039/d6sc00647g","url":null,"abstract":"The quality of perovskite layers is a critical factor in determining the performance of perovskite solar cells (PSCs). α-FAPbI<small>₃</small> is a promising absorber material, but fabricating high quality metastable α-FAPbI<small>₃</small> thin films remains challenging due to poor control over intermediate phases during deposition. Although co-solvent strategies have been identified as an effective method to control these intermediate phases, the underlying mechanism is not fully understood. In this study, we systematically investigate the synergistic effects of DMSO and NMP co-solvents on perovskite mesophase formation, combining theoretical and experimental insights into intermediate phase control and α-FAPbI<small>₃</small> crystallization. Using <em>in situ</em> photoluminescence (PL) monitoring during spin-coating, together with density functional theory (DFT) calculations and Fourier-transform infrared (FTIR) spectroscopy, we reveal how solvent competition modulates intermediate complex formation and evolution. The synergistic effect of these solvents was finally disclosed, which effectively governs the formation and evolution of the intermediate phases. The optimized co-solvent system promotes the transformation of intermediates into α-FAPbI<small>₃</small> at lower thermodynamic transition temperatures, yielding high phase purity and low defect density. As a result, PSCs fabricated using this approach achieved a power conversion efficiency (PCE) of 22.80% with improved stability. The insights gained from this work provide a rational framework for solvent selection in the fabrication of high-quality perovskite films for advanced photovoltaics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147726499","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":"Acridinium amidate as a hydrogen-bonding photocatalyst for direct decarboxylative alkylation of native carboxylic acids","authors":"Duc An Truong, Soichiro Mori, Taiki Ninomiya, Ryoya Niwa, Bumpei Maeda, Haruka Fujino, Masayuki Inoue, Kohsuke Ohmatsu, Takashi Ooi","doi":"10.1039/d6sc00657d","DOIUrl":"https://doi.org/10.1039/d6sc00657d","url":null,"abstract":"The direct generation of carbon radicals from carboxylic acids under visible-light photocatalysis offers an appealing strategy for molecular diversification. Here, we report a decarboxylative Giese-type addition using a zwitterionic acridinium amidate as a uniquely effective photocatalyst, which enables the efficient and selective activation and functionalization of a broad range of carboxylic acids without an external base or oxidant. The catalytic process relies on the formation of a hydrogen-bonded complex between the carboxylic acid and amidate, which triggers proton-coupled electron transfer upon photoexcitation to generate the corresponding carboxyl radical. This method featuring neutral conditions demonstrates excellent functional group tolerance and is applicable to structurally demanding substrates, including complex natural products and pharmaceutically relevant compounds.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147739426","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":"Electrochemically Driven Strain-Release Dearomative (3+2) Cyclization for the Synthesis of Bicyclo[2.1.1]hexane-Fused Polycyclic Spiroindolines","authors":"Yanren Zhu, Enfan Pu, Shaoxiong Yang, Dongbo Zhao, Qi Xu, Piaopiao Jiang, Xiong Li, Hongbin Zhang, Jingbo Chen","doi":"10.1039/d6sc01271j","DOIUrl":"https://doi.org/10.1039/d6sc01271j","url":null,"abstract":"Spiroindolines are ubiquitous structural motifs in natural products and biologically active compounds, making the development of reliable synthetic methods for their construction highly important to the synthetic chemistry community. Moreover, the synthesis of polycyclic compounds featuring C(sp3)-rich and complex three-dimensional (3D) architectures and multiple contiguous quaternary carbon centers in a single step remains a formidable challenge. Herein, we report an efficient and environmentally friendly electrochemical strategy for a dearomative (3+2) cyclization reaction of C3-bicyclo[1.1.0]butane (BCB)-substituted indoles. This method enables the efficient assembly of structurally complex and novel bicyclo[2.1.1]hexane (BCH)-fused polycyclic spiroindolines in high yields, featuring four contiguous stereogenic centers, two of which are spirocyclic all-carbon quaternary carbon centers. This new methodology provides a series of valuable spiroindolines under mild reaction conditions in a practical and atom-economic manner without the need for external oxidants, and the products can be further transformed into more complex spiroindolines. Notably, these C(sp³)-rich products exhibit significant potential in the field of medicinal chemistry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147726498","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":"Anchoring and activation of catalytic sites on the clusters via intermolecular interactions","authors":"Feng Qian, Zhihang Zhao, Baoyu Huang, Zhixiang Xue, Qinzhen Li, Sha Yang, Jinsong Chai, Manzhou Zhu","doi":"10.1039/d6sc00514d","DOIUrl":"https://doi.org/10.1039/d6sc00514d","url":null,"abstract":"Constructing catalytically active sites on the clusters is a mainstream strategy to optimize their catalytic properties. However, it generally leads to unpredictable variations due to the notoriously sensitive relationship between the adduct group and the structure of metal nanoclusters. In this study, a strategy within Au–Cd bimetallic clusters was proposed to achieve controllable modification of the cluster surface through Lewis acid-base specific binding between the recognition group and the cluster, thereby forming Au-Cd-pyridine units. Taking the ORR as a model reaction, the results show that the formed Au-Cd-pyridine catalytic sites can significantly enhance the catalytic activity. Further, we explored the catalytic mechanism using ESI-MS, XPS, and SC-XRD, as well as DFT calculations, and revealed that the ternary catalytic centers regulate the adsorption behavior of OOH* intermediates (enhancement and change of adsorption mode from bridge-form to top-form). The pyridine-modified Au27Cd2 catalyst also demonstrates performance enhancement when extending its application to other electrocatalytic reactions, i.e. NO3RR and HER. Finally, the Au16Cd3 cluster, which contained the Au-Cd-pyridine motifs, was prepared to confirm further the key role of Au-Cd-pyridine binding in enhancing catalytic activity","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147719771","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":"Capturing Elusive Alkenyl Radicals in Wharton Reaction and Its Interrupted Cyclization","authors":"Kornkamon Akkarasereenon, Yichen Liu, Yin Tung Lai, Rongbiao Tong","doi":"10.1039/d6sc01519k","DOIUrl":"https://doi.org/10.1039/d6sc01519k","url":null,"abstract":"The Wharton reaction is a widely used transformation in organic synthesis, enabling the conversion of α,β-epoxy ketones into versatile allylic alcohols. Despite its discovery more than 60 years ago, the detailed mechanism has remained elusive and controversial. While the prevailing mechanism involves the intermediate of an alkenyl anion, several sporadic reports have challenged this pathway, instead suggesting the involvement of an alkenyl radical. Yet no direct evidence has been provided for either species. Herein, we report the first direct capture of the elusive alkenyl radical intermediate in the Wharton reaction using well-established radical traps, including TEMPO (a persistent radical scavenger), PhSSPh, Me<small>₃</small>SnSnMe<small>₃</small>, and a vinyl cyclopropane radical clock. These experiments furnish the first unambiguous chemical evidence for the generation of alkenyl radicals and effectively rule out the alkenyl anion pathway. Furthermore, we discovered an interrupted Wharton reaction in which the alkenyl radicals are efficiently intercepted by tethered arenes under the standard Wharton reaction conditions, leading to novel cyclized products. These cycloadducts offer valuable intermediates for the total synthesis of polycyclic diarylheptanoid musellarins.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"6 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147732250","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":"Lattice strained Na-ZnFe2O4 catalyst boosting CO2 hydrogenation to long-chain olefins","authors":"Xinyan Ai, Chengchao Liu, Zhe Li, Yuhua Zhang, Sixu Liu, Haifeng Xiong, Jinlin Li","doi":"10.1039/d6sc00447d","DOIUrl":"https://doi.org/10.1039/d6sc00447d","url":null,"abstract":"Thermo-catalytic hydrogenation of CO<small>₂</small> to fuels and chemicals is an effective way for the utilization of CO<small>₂</small>, yet it faces significant challenges due to the low CO<small>₂</small> conversion and product selectivity. Here, we report a lattice-strained FeZnNa catalyst synthesized via mechanochemical method (FeZnNa-G), showing the high selectivity of C<small>₄₊</small> long-chain olefins (C<small>₄₊</small><small>⁼</small> ) of 64.9% and C<small>₂₊</small><small>⁼</small> of 77.5% at a high CO<small>₂</small> conversion of 47.7%. We found that the lattice-contracted FeZnNa-G catalyst forms Na-enriched ZnO nano-islands on the surface after activation and a Na-ZnO/Fe<small>₅</small>C<small>₂</small> structure with the presence of 97% Fe<small>₅</small>C<small>₂</small>, facilitating the formation of HCOO<small>^*</small> intermediate and enhancing CO<small>₂</small> activation. A high C<small>₄₊</small><small>⁼</small> space-time yield (STY) of 474.9 mg•g<small>_cat</small><small>^-1</small>•h<small>^-1</small> and an extremely low CO selectivity of ~9.1% exhibited the dual-high performance significantly surpassing the previous reports. This use of lattice strained catalyst offers a new strategy for the efficient conversion of CO<small>₂</small> into high-value olefins, and paves the way for the potential industry application in future.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147720024","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":"A Dual-Mode Large Language Model Assistant for On-Surface Reaction via Fine-Tuning and Retrieval-Augmented Generation","authors":"Juan Xiang, Qi Huang, Xinyi Zhang, Tairan Yang, Zhiwen Zhu, Chanyu Li, Liangliang Cai, Qiang Sun","doi":"10.1039/d6sc01168c","DOIUrl":"https://doi.org/10.1039/d6sc01168c","url":null,"abstract":"Surface reactions underpin catalysis, nanomaterials, energy conversion, and molecular-scale fabrication, yet the field suffers from fragmented knowledge dispersed across unstructured literature, hindering systematic analysis and data-driven discovery. Existing chemical databases and language models inadequately capture the domain-specific semantics and experimental parameters unique to on-surface reactions. Here, we present an integrated framework that transforms dispersed surface-chemistry literature into a structured, machine-readable knowledge platform and leverages it to develop a domain-specialized large language model (LLM) assistant for on-surface reactions. We curated and semantically screened hundreds of thousands of publications to construct the surface-chemistry corpus, from which we extracted 44 predefined reaction attributes across more than 44,000 studies of surface reaction. These structured records were used to build both a high-quality reaction database and a domain-specific question–answering dataset. On this basis, we developed a dual-mode LLM system that combines a parameter-efficiently fine-tuned reasoning model with a dual-source retrieval-augmented generation (RAG) framework, enabling both deep inference and verifiable retrieval of experimental parameters. Evaluations demonstrate that the fine-tuned LLM outperforms existing chemistry-oriented language models on surface-chemistry question answering, achieving a Bert-F1 score exceeding 0.8. Incorporation of the RAG framework further improves factual accuracy, completeness, and reasoning consistency by grounding responses in retrieved literature and structured reaction data. Latent-space analyses reveal that domain-specific fine-tuning reorganizes internal representations toward task-oriented coherence. This work establishes a scalable pathway for converting fragmented surface-chemistry knowledge into an intelligent platform, paving the way toward data-driven prediction, experimental planning and automated reasoning in on-surface reactions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"143 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147732243","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":"Xanthene-to-Fluorene Skeletal Editing via Oxygen Deletion Mediated by Boron and Aluminium Radicals","authors":"Emily E Nahon, Gareth Roland Nelmes, Elena Dallerba, Li Feng Lim, Nicholas Cox, Claire Louise McMullin, Massimiliano Massi, Fabian Kallmeier, Jamie Hicks","doi":"10.1039/d6sc01056c","DOIUrl":"https://doi.org/10.1039/d6sc01056c","url":null,"abstract":"Single-atom skeletal editing via selective oxygen deletion from diarylethers remains an underdeveloped transformation, despite its potential to directly access new carbon frameworks. Here, we report a boron- and aluminium-mediated <em>O</em>-deletion reaction that converts xanthene and diphenylether motifs into fluorene and biphenyl architectures through concomitant C–C bond formation. Lithium metal reduction of diamido arylether boron halides affords lithium boryloxy complexes in high yield and on a multigram scale, with both the new C–C bond and terminal B–O⁻ unit formed in a single step via a transient open-shell B(II) intermediate. Hydrolysis furnishes fluorene- and biphenyl-based [1,3,2]diazaborepin-6-ols, representing previously inaccessible boron-containing fluorophores that exhibit high photoluminescence quantum yields. Extension of this strategy to aluminium allows clean hydrolytic release of the organic scaffold and provides a concise, scalable synthesis of functionalised 4,5-diaminofluorenes. These results establish <em>O</em>-deletion as a viable skeletal editing strategy for arylethers and highlight the role of main-group radical intermediates in selective framework reorganisation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147719772","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":"Rational Guest Selection: A General Principle for Stabilizing Multi-Component Luminescent Materials","authors":"Li-Ke Jing, Yue-Yue Chang, He Li, Biao Lv, Guanyu Yang, Zhan-Ting Li, Bo Yang","doi":"10.1039/d5sc09220e","DOIUrl":"https://doi.org/10.1039/d5sc09220e","url":null,"abstract":"The practical deployment of multi-component luminescent materials is universally hampered by the photodegradation of organic guests, a fundamental challenge that conventional host-centric designs struggle to overcome. Herein, we propose a paradigm-shifting strategy termed \"Rational Guest Selection,\" which elevates the intrinsic molecular photostability of emissive guests to a primary design criterion, equal in importance to emission color. This principle is rigorously validated using the first metal-organic framework constructed from europium ions and pillar[6]arene (Eu-P6MOF) as a model host.While a white-light-emitting composite was initially achieved by co-encapsulating Coumarin 6 and Coumarin 1, its emission color shifted significantly under illumination due to the degradation of Coumarin 1. By applying our principle-rationally replacing the unstable Coumarin 1 with the robust perylene dye-we constructed a stable white-light-emitting composite.The generality of this approach is demonstrated by its success in a low-toxicity ethanol solvent. Mechanistic studies reveal that the rigid MOF pores suppress molecular motions associated with non-radiative decay and photodegradation, with the efficacy of this stabilization being dictated by the guest's innate structural rigidity. The \"Rational Guest Selection\" principle established here provides a universal blueprint for designing durable multi-component functional materials, transcending specific hosts and applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"143 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147732244","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":"Local Polarization Strategy for Efficient Sacrificial-free Hydrogen Peroxide Photoproduction","authors":"Donghui Wang, Jin-Gang-Lu Tao, Haiyang Zhang, Po Zhang, Feng Chen","doi":"10.1039/d6sc00783j","DOIUrl":"https://doi.org/10.1039/d6sc00783j","url":null,"abstract":"Photocatalytic production of hydrogen peroxide (H2O2) from water and oxygen under sunlight offers a safe and sustainable alternative to traditional processes. However, the sluggish water oxidation reaction (WOR) often imposes kinetic limitations on the accompanying oxygen reduction reaction (ORR) in pure water systems. This research developed a series of tailored covalent organic frameworks (COFs) with localized polarization features to boost the reaction rates of WOR. By incorporating varying numbers of sp2-hybridized nitrogen atoms into a single benzene ring, a locally polarized electronic environment was established. In particular, the dual sp2-hybridized nitrogen atoms in pyrimidine units induce strong local polarization, which facilitates charge separation and activates adjacent C=C bonds as more favorable site for WOR. Together with the highly efficient ORR activity enabled by the two nitrogen atoms, the pyrimidine-functionalized TpDa demonstrates outstanding performance in a sacrificial-agent-free system, achieving an H2O2 production rate of 6.94 mmol g-1 h-1 and an apparent quantum yield (AQY) of 25.2%. This work establishes local polarization engineering as an effective strategy for optimizing COFs photocatalysts and highlights its potential for solar-driven chemical transformations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147726501","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}