Hao Wang,Huihui Zhang,Marta Martínez-Belmonte,Jordi Benet-Buchholz,Ruben Martin
{"title":"Regiodivergent Interrupted Ni-Catalyzed Chain-Walking of Unsaturated Alcohol Side-Chains via Traceless Activating Groups.","authors":"Hao Wang,Huihui Zhang,Marta Martínez-Belmonte,Jordi Benet-Buchholz,Ruben Martin","doi":"10.1021/jacs.5c09426","DOIUrl":"https://doi.org/10.1021/jacs.5c09426","url":null,"abstract":"Herein, we describe a regiodivergent interrupted chain-walking of unsaturated aliphatic alcohols. The method leverages the potential of traceless groups to forge C(sp3)-C(sp3) and C(sp3)-nitrogen bonds at distal methylene sp3 C-H sites, with site selectivity dictated by a judicious choice of the ligand. The protocol is distinguished by its broad applicability, offering unconventional disconnections to access β/γ-substituted aliphatic alcohols that are difficult to reach otherwise.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"13 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737296","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}
Leon Gomm,Hui Zhu,Gregor Schnakenburg,Senada Nozinovic,Stefan Grimme,Connie C Lu
{"title":"Reversible C-H Bond Activation of Unactivated Arenes by a Nickel-Silylene Complex.","authors":"Leon Gomm,Hui Zhu,Gregor Schnakenburg,Senada Nozinovic,Stefan Grimme,Connie C Lu","doi":"10.1021/jacs.5c10922","DOIUrl":"https://doi.org/10.1021/jacs.5c10922","url":null,"abstract":"A nickel-silylene complex is shown to reversibly activate benzene via C-H bond activation at ambient temperature. The benzene C-H bond formally adds across the Ni-Si core to form a nickel-silyl complex with an H-Si-Ni-Ph linkage bearing a highly covalent Ni-Si bond (2.2363(6) Å). Dissolution of this product in neat arene solvent, e.g., toluene, trifluorotoluene, or anisole, resulted in the complete conversion to the aryl C-H activated product of the solvent and, thereby, demonstrates the facile reversibility of C-H bond activation across the Ni-Si core. The various arene C-H bond activations by the reactive Ni(0)-silylene species were investigated using density functional theory calculations. In all cases, the arene initially forms an η2-adduct to Ni(0), and then C-H activation proceeds via a concerted oxidative addition at only the Ni center. The Si center assists C-H bond activation by sharing the redox burden with Ni while stabilizing the resultant hydride.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"25 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737323","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}
Eman M Bu Ali, Arnau Bertran, Gabriel Moise, Shuangqing Wang, Rachel C Kilbride, John E Anthony, Claudia E Tait, Jenny Clark
{"title":"Intersystem Crossing Outcompetes Triplet-Pair Separation from <sup>1</sup>(TT) below 270 K in Anthradithiophene Films.","authors":"Eman M Bu Ali, Arnau Bertran, Gabriel Moise, Shuangqing Wang, Rachel C Kilbride, John E Anthony, Claudia E Tait, Jenny Clark","doi":"10.1021/jacs.5c00001","DOIUrl":"https://doi.org/10.1021/jacs.5c00001","url":null,"abstract":"<p><p>Singlet fission (SF) and triplet-triplet annihilation (TTA) are processes which may be exploited to boost the efficiency of solar energy technology. Despite being studied since the late 1960s, the mechanism of singlet fission is still not fully understood. This is partly because the main technique used to study singlet fission, optical or visible/near-IR transient absorption spectroscopy, cannot distinguish between the strongly coupled triplet-pair state <sup>1</sup>(TT), weakly interacting triplet pairs (T..T), and independent triplet states T<sub>1</sub> + T<sub>1</sub>. To solve this problem, we combine transient optical spectroscopy performed as a function of magnetic field and transient electron spin resonance (ESR) spectroscopy to probe the different steps involved in the singlet fission mechanism. By using transient photoluminescence spectroscopy performed as a function of magnetic field to selectively probe the second step of singlet fission: <sup>1</sup>(TT) ⇌ (T..T), we show that in a well-studied model system, anthradithiophene (diF-TES-ADT), this step is highly temperature-dependent, even though the first step, <sup>1</sup>S → <sup>1</sup>(TT), is not. Transient ESR measurements confirm the absence of singlet fission at temperatures between 40 and 250 K for this system, with clear signatures of triplets generated by intersystem crossing and evidence for decay by triplet-triplet annihilation, further supported by magnetic field effect measurements. We conclude that in polycrystalline diF-TES-ADT, intersystem crossing outcompetes triplet hopping at temperatures below 270 K, enabling direct intersystem crossing from the bound triplet pair <sup>1</sup>(TT) to an independent triplet state T<sub>1</sub> localized on a single chromophore. The generated triplets can re-encounter and decay through triplet-triplet annihilation.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144751757","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":"","authors":"Yawen Yang, Pei Liu, Xi-Yang Cui, Junjie Wu, Wenfeng Cai, Jie Cheng, Chuanjie Lu, Xiaowei Fan, Youming Zhang, Zhibo Liu* and Yizhen Yin*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 30","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/jacs.5c10625","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pan Ran, Mingzi Sun, Aoqian Qiu, Xiao Han, Bailin Tian, Beiyao Xiang, Fangyuan Wang, Xinrui Xu, Luhan Dai, Haowen Zhang, Yang Lv, Yue Lin*, Bolong Huang* and Mengning Ding*,
{"title":"","authors":"Pan Ran, Mingzi Sun, Aoqian Qiu, Xiao Han, Bailin Tian, Beiyao Xiang, Fangyuan Wang, Xinrui Xu, Luhan Dai, Haowen Zhang, Yang Lv, Yue Lin*, Bolong Huang* and Mengning Ding*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 30","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/jacs.5c04028","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"","authors":"Qiao-Fei Xu, Xin-Yang Liu, Ruo-Tong Wu, Ming-Yang Fu, Man-Ting Chen, Jun-Sen Xiang, Yin-Shan Meng, Tao Liu*, Pei-Jie Sun*, La-Sheng Long* and Lan-Sun Zheng, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 30","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/jacs.5c10483","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaofeng Zhang, Shiguo Fu, Lei Jia, Bang Hou, Yong Cui* and Yan Liu*,
{"title":"","authors":"Xiaofeng Zhang, Shiguo Fu, Lei Jia, Bang Hou, Yong Cui* and Yan Liu*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 30","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/jacs.5c06460","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Joshua M. Lawrence, Rachel M. Egan, Laura T. Wey, Karan Bali, Xiaolong Chen, Darius Kosmützky, Mairi Eyres, Lan Nan, Mary H. Wood, Marc M. Nowaczyk, Christopher J. Howe* and Jenny Z. Zhang*,
{"title":"","authors":"Joshua M. Lawrence, Rachel M. Egan, Laura T. Wey, Karan Bali, Xiaolong Chen, Darius Kosmützky, Mairi Eyres, Lan Nan, Mary H. Wood, Marc M. Nowaczyk, Christopher J. Howe* and Jenny Z. Zhang*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 30","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/jacs.5c08519","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720440","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ning Liu, Hanyu Xia, Yue Shi, Kejie Xu, Zhiying Yu, Xianqing Wu, Genping Huang*, Jingping Qu and Yifeng Chen*,
{"title":"","authors":"Ning Liu, Hanyu Xia, Yue Shi, Kejie Xu, Zhiying Yu, Xianqing Wu, Genping Huang*, Jingping Qu and Yifeng Chen*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 30","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/jacs.5c07911","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720446","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"","authors":"Ya-Ni Yang, Qiu-Yang Wan, Meng-Jie Zhu, Hua-Yang Ru, Ji-Kun Yang, Qi Li, Meng Zhou, Gaosong Chen*, Yuchen Wu, Lei Jiang and Shuang-Quan Zang*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 30","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/jacs.5c09304","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720455","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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