Chemical Science最新文献

'Trading' C=C Moiety for Four C-O bonds and a Peroxide: Combining Ozone and O-Nucleophiles for Peroxidative Ring Expansion of Cycloalkenes into Medium-Sized 1,2-Dioxacycloalkanes 4个C- o键和一个过氧化物的C=C部分的“交易”：将臭氧和o亲核试剂结合，使环烯烃的过氧化环扩张成中型的1,2-二氧环烷烃

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-10 DOI: 10.1039/d5sc06768e

Roman A Budekhin, Dmitri I Fomenkov, Alexander O. Ustyuzhanin, Darya Y Sliguzova, Ksenia V Skokova, Vera A. Vil', Igor Alabugin, Alexander Olegovich Terent'ev

{"title":"'Trading' C=C Moiety for Four C-O bonds and a Peroxide: Combining Ozone and O-Nucleophiles for Peroxidative Ring Expansion of Cycloalkenes into Medium-Sized 1,2-Dioxacycloalkanes","authors":"Roman A Budekhin, Dmitri I Fomenkov, Alexander O. Ustyuzhanin, Darya Y Sliguzova, Ksenia V Skokova, Vera A. Vil', Igor Alabugin, Alexander Olegovich Terent'ev","doi":"10.1039/d5sc06768e","DOIUrl":"https://doi.org/10.1039/d5sc06768e","url":null,"abstract":"Despite the long and rich history of C=C double bond ozonolysis, ozonolysis of cyclic alkenes has generally been limited to the formation of ring-opening products and fragmentary evidence of the unstable ozonides formation. We present a nonorthodox cycloalkene ring expansion reaction involving ozone and O-nucleophiles, which results in the formation of mediumsized peroxycycles. The mechanism is governed by a delicate balance: the cyclic structure of the substrate dictates conformational restrictions in the generated carbonyl oxide intermediate that kinetically retard the rapid [3+2] cycloaddition between the carbonyl and carbonyl oxide groups, enabling competitive trapping of the carbonyl oxide intermediate by an external O-nucleophile. Some of the synthesized peroxides exhibit ring-chain tautomerism, existing in either a hydroperoxide or a cyclic peroxy hemiacetal form. The use of hydroperoxides as O-nucleophiles leads to compounds containing both cyclic and exocyclic peroxide fragments. Additionally, these unique bisperoxides demonstrate an intriguing reactivity, undergoing a highly selective rearrangement under basic conditions, which affects only one of the peroxide fragments. The developed peroxidative ring expansion of cycloalkenes via ozonolysis broadens the synthetic potential of classical ozonolysis and provides a new pathways for constructing structurally diverse peroxides and polyfunctionalized products of their transfornations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"121 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255477","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}

引用次数: 0

Sustainable chemical science and engineering: celebrating the 130th anniversary of Tianjin University 可持续化学科学与工程：庆祝天津大学建校130周年

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-10 DOI: 10.1039/d5sc90214b

Jinlong Gong, Yingjin Yuan, Naiqin Zhao, Shi-Zhang Qiao

引用次数: 0

Unraveling the Role of Counter-Cations in the Pd-Catalyzed Carbox-ylic Acid C-H Activation 反阳离子在pd催化羧酸C-H活化中的作用

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-10 DOI: 10.1039/d5sc06297g

Zhewei Li, Yan-Hui Tang, Ming Lei

{"title":"Unraveling the Role of Counter-Cations in the Pd-Catalyzed Carbox-ylic Acid C-H Activation","authors":"Zhewei Li, Yan-Hui Tang, Ming Lei","doi":"10.1039/d5sc06297g","DOIUrl":"https://doi.org/10.1039/d5sc06297g","url":null,"abstract":"The counter-cation effect has been proved by experiments to be very crucial in the Pd-catalyzed C-H activation of carboxylic acid but its mechanism is still unclear. In this study, the reaction mechanism of the Pd-catalyzed mono-selective β-C(sp 3 )-H heteroarylation of free carboxylic acids was investigated by density functional theory (DFT) method and the role of the counter-cation effect in this reaction was unveiled. Different from the general understanding that the dimeric or trimeric palladium species are the most stable forms, the calculated results indicate that the dimeric palladium species tend to dissociate into monomers under the assistance of counter-cations, and then form a more stable κ 1 coordination palladium species with carboxylic acids rather than κ 2 coordination palladium species. This enables Pd center to activate the target C-H bond effectively and successfully. In the following C-C coupling process, the Pd-Ag-K catalytic model was proposed, which could drive the C(sp 3 )-H (hetero)arylation of free carboxylic acids instead of the Pd-Ag synergistic model. The critical role of base is to stabilize heterodimeric Pd(II)-Ag(I) species. Moreover, this model successfully explains the origin of the monoselective β-C(sp 3 )-H heteroarylation observed in experiments, in that the Pd(IV) species formed by the oxidative addition are too stable, thus preventing the reductive elimination in the second β-C(sp 3 )-H heteroarylation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"68 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255497","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}

引用次数: 0

The Rise of Rubber-Like Synthetic Polymers in Next-Gen Transistor Technologies 新一代晶体管技术中类橡胶合成聚合物的兴起

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-10 DOI: 10.1039/d5sc05680b

Livy Laysandra, Dinda Bazliah, Daniel Muara Sentosa, Ayu Cahyarani Heksa, Hai Khue Bui, Yu-Cheng Li, Yu-Cheng Chiu

{"title":"The Rise of Rubber-Like Synthetic Polymers in Next-Gen Transistor Technologies","authors":"Livy Laysandra, Dinda Bazliah, Daniel Muara Sentosa, Ayu Cahyarani Heksa, Hai Khue Bui, Yu-Cheng Li, Yu-Cheng Chiu","doi":"10.1039/d5sc05680b","DOIUrl":"https://doi.org/10.1039/d5sc05680b","url":null,"abstract":"Integrating rubber-like synthetic polymers into next-generation transistor technologies offers a transformative approach to advancing wearable electronics, positioning these elastomers as ideal substrates and essential companions to conjugated polymers and other active materials. From six distinct types of rubber-like synthetic polymers, this review spotlights polydimethylsiloxane (PDMS) and styrene-ethylene-butylene-styrene (SEBS) as the leading elastomeric polymers propelling wearable transistor innovations. PDMS is highly favored for its exceptional mechanical flexibility, high electrical resistivity, optical transparency, biocompatibility, and compatibility with soft lithography techniques, making it an ideal substrate for skin-like electronics. SEBS stands out as an elastomeric substrate for soft sensor integration due to its unique ability to form nanoconfined and phase-separated layers with semiconducting polymers that maintain high charge mobility under mechanical strain, while its tissue-like softness and mechanical compliance ensure comfort, durability, and suitability for advanced large-area flexible electronics. A comprehensive overview of recent progress in incorporating these elastomers is discussed, ranging from individual layers to fully integrated components into transistor devices. By bridging polymer chemistry with device engineering, it outlines a strategic research roadmap for developing tunable multifunctional rubber-like synthetic polymers to meet the complex performance requirements of emerging wearable transistor technologies. Finally, key technical challenges are identified alongside potential future research directions to support the development of next-generation wearable transistor applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"122 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255495","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}

引用次数: 0

Chiral tether-guided selective synthesis of Dn-symmetric chiral conjugated nanorings 手性链导选择性合成n对称手性共轭纳米环

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-10 DOI: 10.1039/d5sc06445g

Tai An, Jiayao Yao, Zuo Xiao, Qi Yu, Yu Wang, Yueyue Gao, Yixiao Song, zuoxin huang, Zheng Ding, Xinyue Zhang, Yuanpeng Xie, Menglan Lv, Chuantian Zuo, Junqiao Ding, Liming Ding

{"title":"Chiral tether-guided selective synthesis of Dn-symmetric chiral conjugated nanorings","authors":"Tai An, Jiayao Yao, Zuo Xiao, Qi Yu, Yu Wang, Yueyue Gao, Yixiao Song, zuoxin huang, Zheng Ding, Xinyue Zhang, Yuanpeng Xie, Menglan Lv, Chuantian Zuo, Junqiao Ding, Liming Ding","doi":"10.1039/d5sc06445g","DOIUrl":"https://doi.org/10.1039/d5sc06445g","url":null,"abstract":"Chiral conjugated nanorings with Dn symmetry exhibit extraordinary circularly polarized luminescence (CPL) properties due to their unique cylindrical helical conjugated system. However, their synthesis faces challenges such as numerous atropisomers and tedious separation and chiral resolution processes, which severely hinder their development. In this work, we report a chiral tether-guided synthesis strategy. By introducing a strained planar chiral alkyl chain tether into the fused-ring building unit of the nanoring, the energy differences between the various atropisomers of the nanoring are significantly increased. This guides the formation of the thermodynamically most stable Dn-symmetric isomer during synthesis, thus greatly enhancing the selectivity. Four chiral nanorings, D3-(P)-NR1, D4-(P)-NR1, D3-(M)-NR2, and D4-(M)-NR2, as well as their enantiomers, were facilely obtained through this method. All molecules have shown remarkable and stable CPL capability, with a luminescence dissymmetry factor up to 0.076.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"159 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255494","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}

引用次数: 0

Realizing Highly Efficient Electro-Fluorescence with Co-axial Hybrid Local and Charge-transfer (HLCT) Excited State 利用共轴杂化局部和电荷转移激发态实现高效电荧光

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-10 DOI: 10.1039/d5sc06557g

Kuo Yu, Yingbo Lv, Yilong Li, Zirui Wang, Shi-Tong Zhang, Jinbei Wei, Shanfeng Xue, Chenguang Wang, Bing Yang

{"title":"Realizing Highly Efficient Electro-Fluorescence with Co-axial Hybrid Local and Charge-transfer (HLCT) Excited State","authors":"Kuo Yu, Yingbo Lv, Yilong Li, Zirui Wang, Shi-Tong Zhang, Jinbei Wei, Shanfeng Xue, Chenguang Wang, Bing Yang","doi":"10.1039/d5sc06557g","DOIUrl":"https://doi.org/10.1039/d5sc06557g","url":null,"abstract":"In this work, we report two high-performance donor-acceptor (D-A) electro-fluorescent materials DPXZ-PI and DPXZ-PICN with novel co-axial hybrid local and charge-transfer (HLCT) excited state design method. Featuring the direct bonding of strong electron donor diphenoxazine (DPXZ) and weak electron acceptor phenanthroimidazole (PI), the co-axial HLCT state is initially constructed in DPXZ-PI with high photoluminescence quantum yield (PLQY) of 81.74% and a high maximum external quantum efficiency (EQE) of 14.83% in doped organic light-emitting diode (OLED), which is among the best results of the HLCT emitter-based OLEDs. Notably, the co-axial HLCT state is robust upon the introduction of strong electron acceptor cyano-benzene, which allows the increasing of electron mobility in OLED and high EQE of 11.60% in non-doped OLED of DPXZ-PICN. Overall, the co-axial HLCT realizes the increasing of PLQY with maintained exciton utilizing efficiency (EUE) in OLED, which is an effective method for highly-efficient electro-fluorescent materials and devices.Key words: OLED; HLCT; spin-statistics; excited state; EQE.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"110 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255478","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}

引用次数: 0

Structural Effects of Arsine Ligands on C–H Difunctionalization of Thiophene 砷配体对噻吩碳氢二官能化的结构影响

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-10 DOI: 10.1039/d5sc05285h

Akifumi Sumida, Kaisei Yamamoto, Takahiro Iwamoto, Kensuke Naka, Hiroaki Imoto

{"title":"Structural Effects of Arsine Ligands on C–H Difunctionalization of Thiophene","authors":"Akifumi Sumida, Kaisei Yamamoto, Takahiro Iwamoto, Kensuke Naka, Hiroaki Imoto","doi":"10.1039/d5sc05285h","DOIUrl":"https://doi.org/10.1039/d5sc05285h","url":null,"abstract":"Despite their significant potential in organometallic chemistry, the utility of arsines as ligands in transition-metal catalysis remains underexplored relative to their phosphine counterparts. Although the Pd-catalyzed C–H difunctionalization of thiophene proceeds efficiently with triphenylarsine (AsPh3) but fails with conventional phosphine ligands, the synthetic utility of arsine ligands other than AsPh3 has not been explored. In this study, the steric and electronic requirements of the Pd-catalyzed C–H difunctionalization of thiophene are explored using 36 synthesized arsines and nine phosphines. Ligand parameterization reveals that arsines with moderate electron-donating abilities and sufficient steric accessibility were preferred. Notably, the identified steric demand is more readily met by arsines than by phosphines. Furthermore, arsines exhibit superior oxidative stability under reaction conditions that typically oxidize phosphines owing to the high oxophilicity of phosphorus. These experimental and computational findings demonstrate that the use of arsines can expand the scope of transition metal catalysts by enabling access to catalytic spaces that are less accessible with traditional phosphines.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255479","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}

引用次数: 0

Copper-catalyzed stereospecific methoxyboration of styrenes enabled by oxygen umpolung with acetal-based peroxides 铜催化苯乙烯立体定向甲氧硼化与乙醛基过氧化物的氧掺杂

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-10 DOI: 10.1039/d5sc07347b

Kyosuke Fujiwara, Shogo Nakamura, Koji Hirano

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Synthesis of dibenzoarsole derivatives from biarylborates via the twofold formation of C–As bonds using arsenium dication equivalents 用砷化等价物通过C-As键的双重形成从双芳基硼酸盐合成二苯甲油衍生物

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-10 DOI: 10.1039/d5sc05528h

Kazutoshi Nishimura, Hiroki Iwamoto, Yuji Nishii, Koji Hirano

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Installation of Cationic Phosphorous on Dimethyldihydropyrene Photoswitches: Expanding the Atomic Repertoire towards Far-Red Photoswitching in Water 阳离子磷在二甲基二氢芘光开关上的安装：在水中扩展远红色光开关的原子库