Chemical Science最新文献

{"title":"Borinine-FLP Ring Expansion: Isolation of Eight-Membered B–P Rings Bridged by µ2 Chalcogenide and Chloronium Ions","authors":"Nathan C Frey, Samir Sarkar, Diane Amanda Dickie, Andrew Molino, Robert J Gilliard","doi":"10.1039/d5sc02000j","DOIUrl":"https://doi.org/10.1039/d5sc02000j","url":null,"abstract":"Boron–phosphorus (B–P) frustrated Lewis pairs (FLPs) are an important class of compounds for activating various small molecules. Utilizing the ring expansion reactivity of 9-chloro-9-borafluorene, a borinine-based FLP was synthesized. Various main-group cyclopentene derivatives were obtained via the reaction of the FLP with Me3NO, S8, and Se. Subsequent reduction of these species yielded the ring-expanded compounds, each featuring bridging B–E–B (E = O, S, Se) bonds. Similarly, the halide abstraction from the FLP with AgNTf2 led to the formation of a cationic ring-expanded compound with a bridging B–Cl–B motif. This motif constitutes one of the first examples of a boron-stabilized chloronium ion, as verified using in-depth bonding analysis methods. Mechanistic pathways for the reduction- and halide abstraction-mediated ring expansion reactions are proposed with the aid of density functional theory. Electronic structure computations were performed to determine the best representation of bonding interactions in each compound, suggesting phosophorus(V)–chalcogen double bonding and chalcogen–boron(III) dative interactions in the main-group element cyclopentene derivatives.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"230 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933417","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":"Synthesis of gem-Di(boryl)cyclopropanes from Non-Activated Olefins via Mn-Photocatalyzed Atom Transfer Radical Addition","authors":"Jiefeng Hu, Kun Zhang, Jing Wang, Mingming Huang, Shuangru Chen, Zhuangzhi Shi, Todd B Marder","doi":"10.1039/d5sc02670a","DOIUrl":"https://doi.org/10.1039/d5sc02670a","url":null,"abstract":"The application of gem-diboryl cyclopropanes as versatile building blocks for enhancing molecular complexity has been limited, despite the availability of a few synthetic methods. Herein, we disclose a practical and versatile manganese-catalyzed protocol that enables the synthesis of gem-di(boryl)cyclopropanes from non-activated alkenes in combination with (diborylmethyl)iodides. This photoinduced strategy displays good functional-group tolerance, and encompasses a wide range of applicable substrates, making it applicable to the late-stage modification of natural products. Mechanistic experiments suggest that the reaction proceeds via an intermolecular halogen-atom transfer radical addition, followed by deprotonative alkylation with lithium diisopropylamide, ultimately yielding cyclization products. The versatility and practicality of this approach are further highlighted by the successful implementation of several transformations, which provide an expedited route for synthesizing highly functionalized molecules.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933433","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 Coordination Geometry within Cobalt Spinel Oxides Mediates Photoinduced Polaron Formation","authors":"Erica P. Craddock, Jacob L. Shelton, Michael T Ruggiero, Kathryn E Knowles","doi":"10.1039/d5sc01909e","DOIUrl":"https://doi.org/10.1039/d5sc01909e","url":null,"abstract":"Understanding the photophysics of transition metal oxides is crucial for these materials to realize their considerable potential in applications such as photocatalysis and optoelectronics. Recent studies suggest that formation of localized excited states consisting of polarons (quasi-particles comprising a charge carrier strongly coupled to a proximal lattice distortion) plays a crucial role in the photophysics of these materials. Cobalt-containing spinel oxides (Co<small>₃</small>O<small>₄</small> and ZnCo<small>₂</small>O<small>₄</small>) offer a unique opportunity to investigate the influence of local geometry, and cation inversion on photoinduced polaron formation. Here, we use Hubbard-corrected density functional theory (DFT+U) paired with resonance Raman and temperature-dependent optical spectroscopies to demonstrate that low-energy transitions observed in Co<small>₃</small>O<small>₄</small> are associated with d-d transitions involving cobalt ions occupying tetrahedral sites within the spinel lattice. These low-energy optical transitions exhibit strong coupling to phonon modes associated with tetrahedral sites. Replacing most tetrahedral cobalt ions with zinc produces the slightly inverted ternary spinel material, ZnCo<small>₂</small>O<small>₄</small>, in which we observe a phonon-coupled optical transition that occurs at the same energy as observed in Co<small>₃</small>O<small>₄</small>. We propose that these phonon-coupled optical transitions enable direct access to a polaronic state upon photoexcitation; however, the intensity of this optical transition depends on temperature in Co<small>₃</small>O<small>₄</small>, whereas no significant temperature dependence is observed in ZnCo<small>₂</small>O<small>₄</small>. We therefore hypothesize that in Co<small>₃</small>O<small>₄</small> the mechanism of polaron formation is coupling of the optical transition to dynamic, thermally-gated lattice distortions, whereas, in ZnCo<small>₂</small>O<small>₄</small>, the transition couples to static lattice defects that arise from the presence of a small population of tetrahedrally-coordinated cobalt ions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"67 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933360","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 Design of Circularly Polarized Luminescence Active Chiral Metal-organic Frameworks for Logic Device","authors":"Hongrui Zheng, Qingqing Wang, Fei Wang, Shangda Li, Jian Zhang","doi":"10.1039/d5sc02334c","DOIUrl":"https://doi.org/10.1039/d5sc02334c","url":null,"abstract":"Chiral metal-organic frameworks (CMOFs) have garnered significant attention for their remarkable potential in circularly polarized luminescence (CPL) applications. This study employs circularly polarized fluorescence energy transfer (CPF-ET) as a pivotal strategy for engineering CPL-active CMOFs. Three pairs of structurally analogous CMOFs (<strong>L/D-1</strong>, <strong>L/D-2</strong>, and <strong>L/D-3</strong>) were synthesized by coupling homochiral imidazolium dicarboxylates (L/D-H₂IDPA) with terephthalic acid (TPA) derivatives. These CMOFs displayed distinctive fluorescence and persistent afterglow phosphorescence. As anticipated, these compounds demonstrated outstanding CPL performances, with |g<small>_lum</small>| values reaching up to 0.55 in their single-crystal form. Mechanistic studies revealed a strong correlation between the asymmetry factor and CPF-ET efficiency. These extraordinary CPL properties were leveraged for groundbreaking applications, such as chiral logic devices for sophisticated information encryption. This work lays a robust theoretical and practical foundation for advancing CPL-active materials and seamlessly integrating them into state-of-the-art optoelectronic technologies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"34 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933364","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":"Activation of Perfluoro(methyl vinyl ether) at Rh(I) Complexes: Metal-Centered Versus Phosphine-Mediated Decarbonylation","authors":"Soodeh Mollasalehi, Mike Ahrens, Thomas Braun","doi":"10.1039/d5sc02056e","DOIUrl":"https://doi.org/10.1039/d5sc02056e","url":null,"abstract":"This study investigates the reactivity of perfluoro(methyl vinyl ether) [PMVE, CF<small>₂</small>=CF(OCF<small>₃</small>)] towards rhodium(I) phosphine complexes. The reaction pathways are characterized by C-O and C-F bond cleavage reactions and decarbonylation steps. On using the complex [Rh(H)(PEt<small>₃</small>)<small>₃</small>] (<strong>1</strong>), unprecedented reactivity pathways were observed that distinguish of those found for previously studied fluoroolefins. Reactivity of an excess PMVE at Rh is initiated by coordination to the Rh center in <strong>1</strong>, followed by its insertion into the Rh-H bond and a <em>b</em>-OCF<small>₃</small> elimination. This process ultimately results in OCF<small>₃</small> ligand transformation to give <em>trans</em>-[Rh(F)(CO)(PEt<small>₃</small>)<small>₃</small>] (<strong>4</strong>) and Et<small>₃</small>PF<small>₂</small>. Reactions of stoichiometric amounts of PMVE with [Rh(H)(PEt<small>₃</small>)<small>₃</small>] (<strong>1</strong>) or excess amount of it with [Rh(F)(PEt<small>₃</small>)<small>₃</small>] (<strong>6</strong>) led to olefin complex formation to yield <em>trans</em>-[Rh(F)(<em>η</em><small>²</small>-CF<small>₂</small>CFH)(PEt<small>₃</small>)<small>₂</small>] (<strong>7</strong>) and <em>trans</em>-[Rh(F)(CF(OCF<small>₃</small>)CF<small>₂</small>)(PEt<small>₃</small>)<small>₂</small>] (<strong>8</strong>), respectively. In contrast, a remarkable insertion into the Rh-F bond at [Rh(F)(CO)(PEt<small>₃</small>)<small>₂</small>] (<strong>4</strong>) was observed leading to the formation of <em>trans</em>-[Rh(CO)(CF(OCF<small>₃</small>)CF<small>₃</small>)(PEt<small>₃</small>)<small>₂</small>] (<strong>5</strong>). Decarbonylation of PMVE proceeds not only at Rh, but also via a metal-free, phosphine-mediated process. The latter is characterized by oxidative addition of PMVE at PEt<small>₃</small> to form the fluorophosphoranes <em>E/Z</em>-(F<small>₃</small>CO)CF=CF(PFEt<small>₃</small>), which subsequently convert into Et<small>₃</small>PF<small>₂</small>, CO and presumably tetrafluoroethene.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933319","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":"Modified Chlorophyll Pigment at ChlD1 Tunes Photosystem II Beyond the Red-Light Limit","authors":"Friederike Allgöwer, Abhishek Sirohiwal, Ana Gamiz Hernandez, Maximilian C. Pöverlein, Andrea Fantuzzi, Alfred William Rutherford, Ville Kaila","doi":"10.1039/d4sc07473d","DOIUrl":"https://doi.org/10.1039/d4sc07473d","url":null,"abstract":"Photosystem II (PSII) is powered by the light-capturing properties of chlorophyll a pigments that define the spectral range of oxygenic photosynthesis. Some photosynthetic cyanobacteria can acclimate to growth in longer wavelength light by replacing five chlorophylls for long wavelength pigments in specific locations, including one in the reaction center (RC) (Science 2018, 360, 1210-1213). However, the exact location and the nature of this long wavelength pigment still remain uncertain. Here we have addressed the color-tuning mechanism of the far-red light PSII (FRL-PSII) by excited state calculations at both the ab initio correlated (ADC2) and linear-response time-dependent density functional theory (LR-TDDFT) levels in combination with large-scale hybrid quantum/classical (QM/MM) simulations and atomistic molecular dynamics. We show that substitution of a single chlorophyll pigment (ChlD1) at the RC by chlorophyll d leads to a spectral shift beyond the far-red light limit, as a result of the protein electrostatic, polarization and electronic coupling effects that reproduce key structural and spectroscopic observations. Pigment substitution at the ChlD1 site further results in a low site energy within the RC that could function as a sink for the excitation energy and initiate the primary charge separation reaction, driving the water oxidation. Our findings provide a basis for understanding color-tuning mechanisms and bioenergetic principles of oxygenic photosynthesis at the far-red light limit.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"6 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933365","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":"An amine electrolyte additive with claw structure promoting the stability of a Zn anode in aqueous batteries","authors":"Xiaoqi Sun, Hongtu Zhan, Qianrui Li, Kuo Wang","doi":"10.1039/d4sc06373b","DOIUrl":"https://doi.org/10.1039/d4sc06373b","url":null,"abstract":"The Zn metal anode in aqueous Zn batteries suffers a number of challenges, including dendritic deposition and parasitic reactions. Here, we present a facile interface regulation strategy using a low concentration of electrolyte additive of 0.5 wt% tris(3-aminopropyl)amine (TAA). The TAA molecule exhibits a claw structure with an electronegative amino site at each end. It allows a strong anchorage on the surface of Zn and regulation of Zn<small>²⁺</small> solvation structures near the interface. This allows easier removal of solvated water, but makes final TAA removal more difficult, thereby suppressing side reactions and controlling deposition kinetics. Furthermore, the TAA molecule exhibits strong affinity on the (100) plane of Zn which is twice of the one on (002). It promotes a preferred growth orientation and generates uniform deposits. Benefitting from the above positive effects of the TAA additive, the cycle life of a Zn symmetric cell extends to 8.6 times that in the baseline electrolyte. The cycle life of a full battery using a commercial V<small>₂</small>O<small>₅</small> cathode is also effectively increased.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"118 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933358","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":"Tunable luminescence of hyperbranched polysiloxanes by nonsaturation-induced electrostatic potential polarization for activatable fluorescent theranostics","authors":"Yan Zhao, Zhixuan Feng, Miaomiao He, Xiangyi Wang, Weixu Feng, Wei Tian, Hongxia Yan","doi":"10.1039/d5sc01009h","DOIUrl":"https://doi.org/10.1039/d5sc01009h","url":null,"abstract":"Developing high-efficiency luminescent polysiloxanes with activatable fluorescent theranostics is highly desirable in biomedicines. In this work, we compared hyperbranched polysiloxanes (HBPSis) with diverse nonsaturation and built an intelligent chemodynamic therapy (CDT) system with activatable fluorescence imaging. Experimental characterizations and theoretical calculations reveal that the increased nonsaturation offers numerous delocalized π electrons to renovate the polarization of electrostatic potential, which further drives the clusterization of carbonyl groups. Consequently, the through-space interactions are enhanced, leading to a red-shifted emission and improved quantum yield. Furthermore, an intelligent CDT system, HBPSi-Fe3+@AT, is fabricated. Both the CDT process and the fluorescence imaging can be activated in the presence of overexpressed glutathione. This work gains fresh insight into the nonsaturation-induced electrostatic potential polarization and presents an activatable CDT system for versatile fluorescence imaging-guided theranostics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933432","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":"Fabrication of Low-dimensional Network Polymers with Thermoresponsive Properties Using MOF Scaffolds","authors":"Yuki Kametani, Ami Nishijima, Shu Hiramoto, Takashi Uemura","doi":"10.1039/d5sc02118a","DOIUrl":"https://doi.org/10.1039/d5sc02118a","url":null,"abstract":"Materials with ultimately thin (2D) or narrow (1D) structures have gained significant attention due to their exceptional properties. However, decreasing the dimensionality of soft polymer materials has been a formidable challenge due to the lack of rational synthetic methodology. Here, we performed cross-linking polymerization inside metal–organic frameworks (MOFs) as nanoporous scaffolds to afford poly(<em>N</em>-isopropylacrylamide) (PNIPAm) with unprecedented 1D and 2D network topologies: double strands and monolayer sheets. Remarkably, these polymer networks exhibited unique thermoresponsive properties in water that were strongly correlated with their specific topologies. Note that the transition temperature of double-stranded PNIPAm is among the lowest of known PNIPAm materials. The monolayer PNIPAm sheets exhibit a markedly slow thermal response over a wide temperature range. The dimensional constraint imposed on cross-linking by MOF-templated polymerization enables precisely controlling the chain orientation and proximity, providing new insights into the mechanism of the PNIPAm phase transition.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"30 1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933363","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":"Symmetry-Constrained Generation of Diverse Low-Bandgap Molecules with Monte Carlo Tree Search","authors":"Akshay Subramanian, James Damewood, Juno Nam, Kevin P Greenman, Avni Singhal, Rafael Gomez-Bombarelli","doi":"10.1039/d4sc08675a","DOIUrl":"https://doi.org/10.1039/d4sc08675a","url":null,"abstract":"Organic optoelectronic materials are a promising avenue for next-generation electronic devices due to their solution processability, mechanical flexibility, and tunable electronic properties. In particular, near-infrared (NIR) sensitive molecules have unique applications in night-vision equipment and biomedical imaging. Molecular engineering has played a crucial role in developing non-fullerene acceptors (NFAs) such as the Y-series molecules, which feature a rigid fused-ring electron donor core flanked by electron-deficient end groups, leading to strong intramolecular charge-transfer and extended absorption into the NIR region. However, systematically designing molecules with targeted optoelectronic properties while ensuring synthetic accessibility remains a challenge. To address this, we leverage structural priors from domain-focused, patent-mined datasets of organic electronic molecules using a symmetry-aware fragment decomposition algorithm and a fragment-constrained Monte Carlo Tree Search (MCTS) generator. Our approach generates candidates that retain symmetry constraints from the patent dataset, while also exhibiting red-shifted absorption, as validated by TD-DFT calculations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"49 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143930837","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}