Chemical Science最新文献

{"title":"Double helicene possessing B-N dative bonds built on 1,4-dihydropyrrolo[3,2-b]pyrrole core","authors":"Wojciech Petrykowski, Nicolas Vanthuyne, Carmelo Naim, Francesco Bertocchi, Yevgen P Poronik, Arkadiusz Ciesielski, Michal Ksawery Cyranski, Francesca Terenziani, Denis Jacquemin, Daniel T Gryko","doi":"10.1039/d5sc00540j","DOIUrl":"https://doi.org/10.1039/d5sc00540j","url":null,"abstract":"Just four steps are required to transform 2-nitrobenzaldehyde into centrosymmetric, quadrupolar N,B-doped nanographenes possessing two nitrogen-boron dative bonds. A convergent fragment coupling strategy allowed rapid access to key intermediates bearing the 1,4-dihydropyrrolo[3,2-b]pyrrole core. 2,6-Di-tert-butylpyridine turned out to be the best base for the formation of B←N bonds. This synthetic strategy can be extended to encompass double helicenes possessing two [7]helicene units bearing four five-membered rings. The size of the peripheral arm influences the reaction output: in the case of replacing benzene with dibenzothiophene, the yield decreases from 75% to 16%. Interestingly only two enantiomers and not meso form are formed in the latter case. The obtained double helicene containing 14 fused rings, exhibits green emission characterized by reasonable fluorescence quantum yield reaching 0.38. This dye has average circularly polarized luminescence brightness (BCPL) of about 15 M−1cm−1. The analysis of the electronic structure of the dyes with quantum chemical methods reveals highly-delocalized excited states with the core of the dye acting as a electron-donating moiety.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758564","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":"(3+2)-Cycloaddition of bicyclobutanes and thioketones: access to 2-thiabicyclo[2.1.1]hexanes without the use of catalysts or light","authors":"Daniel B. Werz, Malini George, Daniil A. Knyazev","doi":"10.1039/d5sc00125k","DOIUrl":"https://doi.org/10.1039/d5sc00125k","url":null,"abstract":"A novel approach to the synthesis of the 2-thiabicyclo[2.1.1]hexane scaffold has been described. The method utilizes two highly reactive species: bicycle[1.1.0]butanes (BCBs) and thioketones. Their high reactivity enabled the formation of the desired product to occur under ambient conditions, without the need for catalysts, additives or light irradiation. To the best of our knowledge, this is the first rational synthesis of this specific skeleton. A variety of carbonyl-substituted BCBs, either with or without substituent at the other bridgehead, and thioketones were examined.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"107 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758566","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":"Water-soluble BODIPY dyes: A novel approach for their sustainable chemistry and applied photonics","authors":"Christopher Schad, César Ray, Carolina Díaz-Norambuena, Sergio Serrano, Florencio Moreno Jiménez, Beatriz Lora Maroto, Inmaculada Garcia-Moreno, Mónica Muñoz-Úbeda, Ivan Lopez-Montero, Jorge Bañuelos, Santiago De la Moya","doi":"10.1039/d5sc01295c","DOIUrl":"https://doi.org/10.1039/d5sc01295c","url":null,"abstract":"The BODIPY family of organic dyes has emerged as a cornerstone in photonics research development, driving innovation and advancement in various fields of high socio-economic interest. However, the majority of BODIPY dyes exhibit hydrophobic characteristics, resulting in poor solubility in water and other hydrophilic solvents. This solubility is paramount for their optimal utilization in a myriad of photonic applications, particularly in the realms of biology and medicine. Furthermore, it facilitates safer and more sustainable manipulation and chemical modification of these expansive dyes. Nevertheless, bestowing BODIPYs with water solubility while preserving their other essential properties, notably their photophysical signatures, poses a significant challenge. In this context, we present a straightforward general chemical modification aimed at converting conventional hydrophobic BODIPYs into highly hydrophilic variants, thus enabling their efficient solubilization in water and other hydrophilic solvents with minimal disruption to the dye's inherent photophysics. The efficacy of this methodology is demonstrated through the synthesis of a number of water-soluble BODIPY dyes featuring diverse substitution patterns. Furthermore, we showcase their utility in a spectrum of photonics-related applications, including in-water BODIPY chemistry and dye-laser technology, and fluorescence microscopy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"58 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758651","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":"Diazomethyl-λ3-iodane meets aryne: Dipolar cycloaddition and C-to-N iodane shift leading to indazolyl-λ3-iodanes","authors":"Shinya Otsuki, Kazuya Kanemoto, Daniel Carter Martos, Eunsang Kwon, Joanna Wencel-Delord, Naohiko Yoshikai","doi":"10.1039/d5sc00266d","DOIUrl":"https://doi.org/10.1039/d5sc00266d","url":null,"abstract":"Diazomethyl-λ<small>³</small>-iodanes have recently emerged as carbyne equivalents in organic synthesis, enabling the construction of multi-substituted carbon centers through strategic sequential activation of the diazo and iodane functional groups. Distinct from such reaction modes, we report here on the reactivity of diazomethyl-λ<small>³</small>-iodanes as iodane-bound 1,3-dipoles toward arynes. Equipped with bis(trifluoromethyl)benzyl alcohol-based benziodoxole (BX) moiety, diazomethyl-λ<small>³</small>-iodanes undergo annulation with arynes generated from ortho-silylaryl triflates and cyclic diarylhalonium salts, resulting in indazolyl-λ<small>³</small>-iodanes through [3+2] cycloaddition and carbon-to-nitrogen iodane migration. DFT calculations reveal that diazomethyl-BX prefers [3+2] cycloaddition with aryne over aryne insertion into the carbon–iodine(III) bond (carboiodanation) and that the subsequent iodane migration proceeds through two consecutive 1,5-iodane shifts. The utility of these indazolyl-BXs as indazole-transfer agents has been demonstrated by α-functionalization of <em>N</em>,<em>N</em>-dimethylaniline derivatives.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"73 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758652","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":"The scalable growth of high-performance nanostructured heterojunction photoanodes for applications in tandem photoelectrochemical-photovoltaic solar water splitting devices","authors":"Brian Tam, Sebastian D Pike, Jenny Nelson, Andreas Kafizas","doi":"10.1039/d4sc08595g","DOIUrl":"https://doi.org/10.1039/d4sc08595g","url":null,"abstract":"Due to their complementary absorption characteristics and band energy structure, the BiVO4-coated WO3 heterojunction architecture is commonly employed as a metal oxide photoanode for the water oxidation half-reaction. The energy level ordering results in a staggered heterojunction that can effectively separate photoexcited electrons into the WO3 layer towards the current collector and photoexcited holes into the BiVO4 layer towards the interface with the electrolyte. Chemical vapour deposition (CVD) is an upscalable technique for fabricating large-area thin films of a wide range of semiconductors with nanoscale control. The fluorine-doped tin oxide (FTO)-coated transparent conductive glass substrates used herein are mass-produced by the glass industry with atmospheric pressure CVD and so the entire photoelectrode could be produced in one production process on float glass panels. This work is a detailed study of the use of atmospheric pressure CVD to fully-fabricate high-performance BiVO4-coated WO3 nanostructures (500 – 2000 nm in length with 25 – 100 nm thick BiVO4 coatings) for photoelectrochemical (PEC) water splitting. Incident photon-to-current efficiency measurements were used to calculate optimal solar predicted photocurrents of 1.92 and 2.61 mA.cm-2 (2.3% and 3.2% solar-to-hydrogen efficiency if coupled to a hypothetical photovoltaic providing 1.23 V) for WO3/ BiVO4 heterojunction samples under front and back-illumination, respectively. The heterojunction showed more than additive improvements over the parent materials, with bare WO3 and BiVO4 samples showing 0.68 and 0.27 mA.cm-2 and 0.50 and 0.87 mA.cm-2 under front and back-illumination, respectively. Simulations of the current-voltage characteristics of tandem crystalline silicon photovoltaic modules coupled to the PEC devices were consistent with the solar predicted photocurrents. These promising results for BiVO4-coated WO3 nanoneedles fully-deposited by atmospheric pressure CVD enables future research into photoanodes amenable to large-area scale-up.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"72 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744814","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":"Correlating halide segregation of wide-bandgap perovskites with methoxy group in organic hole-selective materials","authors":"Xiaoyu Ji, Yun Zhao, Xiaofeng Chen, Shuo Zhang, Liqing Zhan, Huidong Zhang, Weizhong Zheng, Weihong Zhu, Yongzhen Wu","doi":"10.1039/d4sc08810g","DOIUrl":"https://doi.org/10.1039/d4sc08810g","url":null,"abstract":"Mixed-halide wide-bandgap (WBG) perovskites are widely used in constructing tandem photovoltaics, but their practical applications are challenged by a phenomenon called photo-induced halide segregation (PIHS), which is detrimental to stability of the devices. The origin of such PIHS is not fully understood yet, restricting their further advancement. Here, we report a serendipitous discovery that PIHS of WBG perovskites is highly related to the presence of methoxy group (MeO) in organic hole-selective materials (HSMs). Based on a model compound with triphenylamine as the hole-selecting group and cyanovinyl phosphonic acid as the anchoring group, we developed a series of HSMs with only difference in substituent groups (MeO, methyl or hydrogen) on the triphenylamine. In-situ photoluminescence (PL) measurements reveal that all MeO carrying HSMs results in severe PIHS and this observation is further validated by commercialized PACz-series HSMs. Temperature dependent PL experiments and density functional theory calculations suggest that contact between MeO group and perovskites reduces diffusion energy barrier of halide ion, thus accelerating the PIHS. Removing MeO group from HSMs not only improves power conversion efficiency of 1.76 eV WBG perovskite solar cells from 19% to 21%, but also enhances operational stability with T90 augmented from 180 h to 650 h. This work discloses molecular structure of HSMs caused PIHS, and suggests to avoid MeO group in designing interfacial materials for WBG perovskites related optoelectronic devices.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"5 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744815","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 bioimmune mechanism-inspired targeted elimination mechanism on the anode interface for zinc–iodine batteries","authors":"Kaixin Wang, Yuting He, Ruduan Yuan, Zhaoyu Chen, Qianzhi Gou, Sida Zhang, Huaping Mei, Yujie Zheng, John Wang, Meng Li","doi":"10.1039/d5sc00040h","DOIUrl":"https://doi.org/10.1039/d5sc00040h","url":null,"abstract":"Alkaline byproducts at the zinc anode interface continue to exacerbate subsequent side reactions, so realizing timely salvage of electrodes is equally important compared to upfront prevention strategies. Although the utilization of acid electrolytes could eliminate by-products on the Zn anode, they inevitably exacerbate the undesired hydrogen evolution reaction. Therefore, achieving elimination of by-products without exacerbating other side reactions is urgently needed. Inspired by the immune protection mechanisms in organisms, facile cysteamine hydrochloride (Cy-H) additives were incorporated into the aqueous electrolyte to stabilize the anode. Concretely, the Cy-H additives can reconstruct the electrical double layer (EDL) on the Zn anode and inhibit drastic parasitic reactions and cooperate with electric fields and acidic environments, thus achieving the desired effect of targeted elimination of alkaline by-products. Ultimately, with a long calendar lifespan of 2000 h with a Zn anode carrying by-products and outstanding performance over 8000 cycles for the Zn‖I<small>₂</small> full cell, the assembled pouch battery also achieved 1000 cycles without capacity degradation. To further promote the practical applications, the inhibition mechanism of Cy-H additives on full-cell self-discharge was revealed. This work provides new insights for the use of strong acid electrolytes and the elimination of interfacial by-products in aqueous zinc–iodine batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744817","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":"Catalytic asymmetric construction of 1,5-remote Si- and C-stereocenters via desymmetrizing ene reaction of bis(methallyl)silanes","authors":"Qiuhui Cao, Yuntian Yang, Yiwen Mei, Minghui Ji, Fei Wang, Xiaoming Feng, Weidi Cao","doi":"10.1039/d5sc01054c","DOIUrl":"https://doi.org/10.1039/d5sc01054c","url":null,"abstract":"Catalytic enantioselective synthesis of chiral silanes has long been a challenging pursuit. Achieving simultaneous construction of remote Si- and C-stereogenic centers in an acyclic molecule via desymmetrization is particularly difficult. Herein, we realized an example of a chiral nickel(II) complex catalyzed desymmetrizing carbonyl-ene reaction of bis(methallyl)silanes with α-keto aldehyde monohydrates, enabling the highly chemo-, diastereo- and enantioselective synthesis of chiral δ-hydroxy silanes featuring 1,5-remote Si- and C-stereocenters. This protocol demonstrated good functional group tolerance and broad substrate scope. Bioactivity study revealed its potential applications for the synthesis of bioactive molecules.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758567","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":"Orbital contributions to magnetically induced current densities using gauge-including atomic orbitals","authors":"Rinat T. Nasibullin, Maria Dimitrova, Rashid Valiev, Dage Sundholm","doi":"10.1039/d5sc00627a","DOIUrl":"https://doi.org/10.1039/d5sc00627a","url":null,"abstract":"We have developed a method to calculate orbital contributions to magnetically induced current density (MICD) susceptibilities in molecules using gauge-including atomic orbitals (GIAO). The methods implemented in the GIMIC program have been used for analyzing orbital contributions to magnetically induced ring-current (MIRC) strengths. We have studied five aromatic, one nonaromatic, and four antiaromatic molecules. We show here that the contributions to the MIRC strength of all orbitals belonging to a given irreducible representation of the molecular point group in the presence of an external magnetic field are divergence free, whereas the MICD susceptibility of the individual orbitals are not generally divergence free. The largest contribution to the MIRC strength of antiaromatic molecules originates from the transition between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), whereas aromatic molecules have significant contributions involving many occupied orbitals. The MIRC contributions of σ orbitals are significant for planar molecules with a strained molecular structure.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"103 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744816","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":"Hierarchical Interface Engineering for Advanced Magnesium-Based Hydrogen Storage: Synergistic Effects of Structural Design and Compositional Modification","authors":"Han Jiang, Zhao Ding, Yuting Li, Guo Lin, Shaoyuan Li, Wenjia Du, Yu'an Chen, Leon L Shaw, Fusheng Pan","doi":"10.1039/d5sc01169h","DOIUrl":"https://doi.org/10.1039/d5sc01169h","url":null,"abstract":"Interface engineering fundamentally revolutionizes magnesium-based hydrogen storage systems by orchestrating atomic-scale interactions and mass transport pathways through precisely engineered structural architectures and chemical environments. This review presents a paradigm-shifting framework that transcends conventional surface modification approaches, establishing interface engineering as a cornerstone strategy for next-generation hydrogen storage materials. Through sophisticated control of interface architecture - from one-dimensional confined channels that facilitate directional hydrogen diffusion, to two-dimensional platforms that maximize catalytic interactions, to three-dimensional networks that optimize spatial organization - we unlock unprecedented control over hydrogen storage dynamics. The strategic modulation of interface chemistry creates synergistic effects between structural features and catalytic functionalities. Metal-metal interfaces orchestrate electron transfer processes and facilitate hydrogen dissociation, while engineered support interfaces maintain structural integrity and enhance cycle life. This multi-level interface control enables simultaneous optimization of thermodynamic destabilization and kinetic enhancement. Advanced characterization and theoretical modeling reveal that the controlled evolution of interface structure during hydrogen cycling plays a pivotal role in determining long-term performance stability. Our comprehensive analysis establishes fundamental correlations between interface architecture and hydrogen storage mechanisms, providing critical insights for rational material design. The review concludes by identifying key challenges and opportunities in translating these interface engineering principles into practical energy storage technologies, offering a roadmap for future development of high-performance magnesium-based hydrogen storage systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744819","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}