Science China Chemistry最新文献

{"title":"Thermally activated delayed fluorescence-active one-dimensional Cu-I coordination polymers for high-resolution X-ray imaging: tuning the singlet-triplet energy gap through halogen engineering","authors":"Bao-Yi Li,&nbsp;Wen-Long Zhou,&nbsp;Peng-Kun Wang,&nbsp;Wen-Fei Wang,&nbsp;Rong Li,&nbsp;Shuai-Hua Wang,&nbsp;Fa-Kun Zheng,&nbsp;Guo-Cong Guo","doi":"10.1007/s11426-025-3206-3","DOIUrl":"10.1007/s11426-025-3206-3","url":null,"abstract":"<div><p>Cu(I) halide scintillators have emerged as promising alternatives to conventional X-ray imaging materials, owing to their high luminescence efficiency, structural tunability, and solution processability. Among them, one-dimensional (1D) Cu-I coordination polymers (CPs) not only possess excellent X-ray absorption performance and structural diversity, but also exhibit enhanced stability attributed to their continuous inorganic chain frameworks. However, low radiative efficiency remains a core bottleneck hindering the optoelectronic applications of 1D copper iodide CPs. In this study, ligand halogen engineering is synergistically integrated with the thermally activated delayed fluorescence (TADF) mechanism: halogen electron-withdrawing effects tune the singlet-triplet energy gap (Δ<i>E</i>_ST), while the heavy atom effect boosts orbital coupling, promoting TADF and enabling efficient exciton harvesting. Additionally, the electron-withdrawing property of halogens can further reduce the repulsion between Cu and I, suppressing non-radiative transitions and thereby synergistically enhancing the optical performance and light conversion efficiency of the materials. Herein, two 1D Cu-I CPs were successfully synthesized by introducing different halogen atoms into the ligands: [CuI(3,5-2Cl-py)]_<i>n</i> (<b>SC-Cl</b>, where 3,5-2Cl-py = 3,5-dichloropyridine) and [CuI(3,5-2Br-py)]_<i>n</i> (<b>SC-Br</b>, where 3,5-2Br-py = 3,5-dibromopyridine). Performance characterizations demonstrate that the light yields of <b>SC-Cl</b> and <b>SC-Br</b> reach 14144.4 and 11005.1 photons MeV⁻¹, respectively. The flexible scintillation screens fabricated from these two materials achieve high spatial resolutions of 18.8 and 16.0 lp mm⁻¹ in X-ray imaging. This work not only provides an effective strategy for optimizing the performance of 1D scintillators but also highlights their potential applications in medical diagnosis and security inspection fields.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"69 7","pages":"3524 - 3531"},"PeriodicalIF":9.8,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148553093","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 a quasi-0D tungsten tellurite nonlinear optical crystal with exceptionally balanced properties","authors":"Shijie Zhao,&nbsp;Lili Li,&nbsp;Tinghui Zhang,&nbsp;Huijian Zhao,&nbsp;Ning Ye,&nbsp;Zhanggui Hu,&nbsp;Conggang Li","doi":"10.1007/s11426-025-3238-y","DOIUrl":"10.1007/s11426-025-3238-y","url":null,"abstract":"<div><p>Transition-metal-oxygen polyhedra and heavy p-block motifs typically undergo polymerization into chains, layers, or three-dimensional networks via corner- or edge-sharing, driven by thermodynamic stability, which makes the isolation of discrete polyhedral units exceptionally challenging. Breaking with this conventional paradigm, we report a dimensionality engineering strategy that disrupts covalent bridging-oxygen networks to achieve the targeted synthesis of a tungsten tellurite nonlinear optical (NLO) crystal, Ca₇(TeO₃)₆(WO₄) (CTWO), which features an unprecedented zero-dimensional (0D) structure composed of fully isolated [WO₄] tetrahedra and [TeO₃] trigonal pyramids. This unique 0D topological configuration endows CTWO with an ultrawide bandgap of 4.62 eV, the largest reported among acentric tungsten tellurites, corresponding to a UV cutoff at 268 nm. Additionally, CTWO exhibits exceptional NLO properties, including strong SHG efficiency of 6.0 × KDP, a high laser-induced damage threshold (LIDT) value of 50 × AGS, a sufficient birefringence of 0.12 at 1064 nm, and extended infrared (IR) cutoffs beyond 7.0 µm. This work not only demonstrates the efficacy of dimensionality control in modulating band structures and enhancing functional properties in mid-IR NLO materials, but also opens a viable pathway for the rational design of isolated functional units in extended solid-state frameworks.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"69 7","pages":"3469 - 3476"},"PeriodicalIF":9.8,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148553065","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":"Copper-catalyzed synthesis of γ-amino acids with indole units via radical dicarbofunctionalization of 2-azadienes","authors":"Shengzu Duan,&nbsp;Ya Du,&nbsp;Lening Zhang,&nbsp;Shuntao Huang,&nbsp;Sina Liu,&nbsp;Xiang Yang,&nbsp;Hongbin Zhang,&nbsp;Patrick J. Walsh,&nbsp;Xiaodong Yang","doi":"10.1007/s11426-025-3157-x","DOIUrl":"10.1007/s11426-025-3157-x","url":null,"abstract":"<div><p>γ-Amino acids have received increasing attention due to their biological activity in natural products and pharmaceuticals. Meanwhile, indole derivatives represent a class of privileged compounds in biological, medicinal, and organic chemistry, with new approaches to their functionalization in demand. A general method for the union of indole and γ-amino acid pharmacophores, however, has not been realized. Herein, we report a novel copper-catalyzed radical dicarbofunctionalization of 2-azadienes with α-bromo carbonyl compounds and indoles. This cascade reaction generates two new C–C bonds in a single step through an intermolecular three-component coupling, providing a wide array of γ-amino acids containing C3-substituted indole units with complete chemo- and regioselectivity (41 examples, 50%–90% yields). This transformation can also be used to elaborate natural products and drug molecules. Mechanistic studies indicate α-carbonyl and 2-azaallyl radicals in a copper-mediated coupling process.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"69 7","pages":"3566 - 3571"},"PeriodicalIF":9.8,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148553064","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":"Photoredox-catalyzed site-selective dearomative cross-coupling of electron-deficient indoles and naphthalenes with electron-rich (hetero)arenes","authors":"Shu-Min Nie,&nbsp;Hao Cui,&nbsp;Bohang An,&nbsp;Ji-Lin Chen,&nbsp;Feng Lan,&nbsp;Shu-Li You,&nbsp;Xiao Zhang","doi":"10.1007/s11426-025-3190-6","DOIUrl":"10.1007/s11426-025-3190-6","url":null,"abstract":"<div><p>(Dearomative) cross-coupling of two (hetero)arenes via single-electron processes without the need for prefunctionalized partners and precious metals represents an attractive strategy for the assembly of (hetero)biaryl or dearomative scaffolds. However, the current known methods predominantly utilize two electron-rich (hetero)arenes as coupling partners. In addition, the inherent obstacle of selectivity issues poses a notable challenge. Here, we report a photocatalytic strategy for site-selective dearomative cross-coupling of electron-deficient indoles and naphthalenes with electron-rich (hetero)arenes. Enabled by an organic photocatalyst-isoazatruxene derivative <b>ITN-2</b>, electron-deficient (hetero)arenes are converted into carbocations through sequential SET reduction, protonation, and SET oxidation. The resulting electrophilic species can then be trapped by a variety of electron-rich (hetero)arenes to furnish the coupling. When electron-deficient indoles serve as the coupling partners, the dearomative cross-coupling takes place at the C3 position with reversed regioselectivity, allowing access to indoline derivatives bearing all-carbon quaternary centers in high yields. In addition, we demonstrate that naphthalene derivatives participate well in an unconventional C4-site-selective dearomative coupling with electron-rich (hetero)arenes. Alternatively, the formal C–H/C–H cross-coupling of electron-deficient and electron-rich (hetero)arenes is accomplished with extraordinary site-selectivity through a one-pot dearomatization/aromatization approach.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"69 7","pages":"3572 - 3579"},"PeriodicalIF":9.8,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148553095","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":"Iron-catalyzed direct synthesis of p-dioxanone from commodity feedstocks methyl glycolate and ethylene oxide","authors":"Zheng Li,&nbsp;Tianqi Li,&nbsp;Dongfang Zhao,&nbsp;Zhibo Li","doi":"10.1007/s11426-025-3173-1","DOIUrl":"10.1007/s11426-025-3173-1","url":null,"abstract":"<div><p>Closed-loop recyclable polymers represent a promising route toward a circular plastic economy, yet their broad applications are constrained by the limited availability of suitable monomers. Poly(<i>p</i>-dioxanone) (PPDO) is a high-performance, closed-loop recyclable polyester, but its application has been hampered by the lack of efficient and scalable synthesis of its monomer, <i>p</i>-dioxanone (pDO). Here, we report the first iron-catalyzed, one-pot synthesis of pDO directly from the commodity feedstocks of methyl glycolate (MG) and ethylene oxide (EO). Iron chloride (FeCl₃) catalyzes a tandem ring-opening reaction between MG and EO to afford methyl 2-(2-hydroxyethoxy)acetate (MHEA), which undergoes intramolecular cyclization to pDO under optimized conditions. This process achieves an isolated yield of up to 66% and furnishes a crystalline pDO monomer that can be readily polymerized into high-molecular-weight PPDO. The method is green, atomeconomical and scalable, providing a practical route to cost-effective production of pDO. This strategy not only enables sustainable access to PPDO but also paves a new approach to the efficient chemical synthesis of cyclic monomers for closed-loop polymer materials.</p><div><figure><div><div><picture><source><img></source></picture><span>The alternative text for this image may have been generated using AI.</span></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"69 6","pages":"3040 - 3048"},"PeriodicalIF":9.7,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148060776","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 inorganic {Co12}-added polyoxometalate octahedral cage: synthesis, structure and catalytic property","authors":"Peng-Yun Zhang,&nbsp;Hai-Lou Li,&nbsp;Zhen-Wen Wang,&nbsp;Juan Chen,&nbsp;Guo-Yu Yang","doi":"10.1007/s11426-025-3160-0","DOIUrl":"10.1007/s11426-025-3160-0","url":null,"abstract":"<div><p>The appealing aesthetic characteristics and distinctive physiochemical properties have driven the continuous pursuit of assembling hollow crystalline cage molecules (CCMs). Herein, we present the first inorganic {Co₁₂}-added polyoxometalate cage Cs₈₅Na₂₀H₁₉₅[{SiW₁₀Co₂O₃₉}₄{SiW₁₀Co₂O₃₆}₂]·85H₂O (<b>1</b>), of which the polyoxoanion is assembled by 4 Keggin-type {SiW₁₀Co₂O₃₉} units and 2 {SiW₁₀Co₂O₃₆} units as the Vertexes and 12 W(Co)–O–W(Co) bonds as the linkers, resulting in a novel hollow cage with octahedral configuration. Intriguingly, the arrangement of 12 Co²⁺ and 12 W⁶⁺ centers within the central [Co₁₂W₁₂O₃₆]²⁴⁺ cage follows a truncated octahedral Archimedean-type tetrakaidecahedron, which resembles the <i>β</i> cage in zeolite structures. Furthermore, <b>1</b> displayed an efficient catalytic performance and satisfactory recyclability in the Knoevenagel condensation with the various benzaldehyde derivatives and malononitrile as substrates.</p><div><figure><div><div><picture><source><img></source></picture><span>The alternative text for this image may have been generated using AI.</span></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"69 6","pages":"2908 - 2912"},"PeriodicalIF":9.7,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148060703","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":"Aqueous battery protocol engineering for terminal hydrogen evolution suppression","authors":"Binghang Liu,&nbsp;Jintao Ma,&nbsp;Youjie Shi,&nbsp;Zhipeng He,&nbsp;Liumin Suo","doi":"10.1007/s11426-025-3269-2","DOIUrl":"10.1007/s11426-025-3269-2","url":null,"abstract":"<div>\u0000<div><figure><div><div><picture><source><img></source></picture><span>The alternative text for this image may have been generated using AI.</span></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"69 5","pages":"2271 - 2275"},"PeriodicalIF":9.7,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147828480","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":"Fluorination of vinylene-linked benzotristhiazole-based covalent organic frameworks for enhanced photocatalytic performance","authors":"Yuancheng Wang,&nbsp;Zhipeng Luo,&nbsp;Wenyu Zhou,&nbsp;Luxi Tan,&nbsp;Xin Zhao,&nbsp;Jialin Cui,&nbsp;Xiong Chen,&nbsp;Yingjie Zhao","doi":"10.1007/s11426-025-3196-3","DOIUrl":"10.1007/s11426-025-3196-3","url":null,"abstract":"<div><p>Vinylene-linked covalent organic frameworks (COFs) are renowned for their excellent organic semiconducting properties, attributed to their in-plane <i>π</i>-conjugated and robust structures. However, their synthesis remains challenging due to the complexity of reaction pathways and the limited availability of building units containing reactive methyl groups, which hinders their practical application. Herein, two vinylene-linked benzotristhiazole-based 2D COFs with high crystallinity were constructed via Aldol condensation reaction. Notably, the incorporation of fluorine atoms into the COF framework significantly enhanced its photocatalytic activity. Specifically, the fluorinated COF (BTZ-F) exhibited substantially improved performance in the selective oxidation of organic sulfides compared to its non-fluorinated counterpart (BTZ-H). A synergistic combination of experimental characterization and theoretical calculations revealed that fluorination significantly modulates the electronic structure of the framework, thereby promoting efficient charge separation and transfer. Further mechanistic investigations revealed that both electron-transfer and energy-transfer pathways are involved in the oxidation of phenyl methyl sulfide, providing deeper insights into the enhanced photocatalytic efficiency of the fluorinated framework.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"69 7","pages":"3626 - 3632"},"PeriodicalIF":9.8,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148560043","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":"Research progress in ionizable cationic lipids in mRNA delivery: from synthetic strategies to applications","authors":"Xinwei Zhang,&nbsp;Yuqin Liao,&nbsp;Xuechuan Hong,&nbsp;Yuling Xiao,&nbsp;Xiaodong Zeng","doi":"10.1007/s11426-025-3182-6","DOIUrl":"10.1007/s11426-025-3182-6","url":null,"abstract":"<div><p>Ionizable cationic lipids (ICLs) constitute the essential core of lipid nanoparticles (LNPs) for safe and efficacious mRNA therapeutics, their design evolving from empirical iterations to rational, modular paradigms that utilize molecular precision for organ-specific delivery. This review delineates advancements in synthetic methodologies, spanning traditional solution-phase routes alongside innovative solid-phase, biocatalytic, and machine learning-driven approaches. We further elucidate how nuanced structural engineering dictates organ-specific mRNA transduction, facilitating selective engagement of neural, pulmonary, splenic, lymphatic, skeletal, and pancreatic tissues. Addressing persistent hurdles in selectivity, formulation resilience, scalable manufacturing, and immune evasion, we propose forward-looking strategies for next-generation ICLs that synergize chemical sophistication with programmable bioactivity, poised to revolutionize precision gene medicine.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"69 7","pages":"3339 - 3357"},"PeriodicalIF":9.8,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148560045","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":"Asymmetric C–H acetoxylation and halogenation of [2.2]paracyclophanes via photoinduced cobalt catalysis","authors":"Liang-Neng Wang,&nbsp;Ke Gao,&nbsp;Bing-Feng Wang,&nbsp;Yue-Liu-Ting Fu,&nbsp;Chu-Han Qu,&nbsp;Siping Wei,&nbsp;Liang-Qiu Lu,&nbsp;Wen-Jing Xiao","doi":"10.1007/s11426-025-3198-2","DOIUrl":"10.1007/s11426-025-3198-2","url":null,"abstract":"<div><p>Chiral [2.2]paracyclophane (PCP) is a valuable scaffold in chiral ligands, catalysts and for materials; however, efficient synthetic methods, particularly those through asymmetric catalytic transformations, remain limited. Herein, we report a photoinduced cobalt-catalyzed asymmetric C–H functionalization to access a diverse range of acetoxylated and halogenated planar chiral PCPs with high efficiency (up to 97% yield) and excellent enantioselectivity (up to 99% ee). The broad utility of the presented approach is demonstrated through drug modification and the synthesis of chiral ligands and aggregation-induced emission-active materials.</p><div><figure><div><div><picture><source><img></source></picture><span>The alternative text for this image may have been generated using AI.</span></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"69 6","pages":"2974 - 2979"},"PeriodicalIF":9.7,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148061085","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}