Chinese Journal of Chemistry最新文献

{"title":"tBuOK/TMSOK-Mediated “Alkyl Halide to Alkyl Free Radical” Transformation for Transition-Metal-Free Benzoin α-C—H Alkylation","authors":"Zhouying Wang,&nbsp;Lu Gan,&nbsp;Zhibin Song,&nbsp;Yunyun Liu,&nbsp;Jie-Ping Wan","doi":"10.1002/cjoc.202400664","DOIUrl":"10.1002/cjoc.202400664","url":null,"abstract":"<div>\u0000 \u0000 <p>The alkali <i>tert</i>-butoxide (^<i>t</i>BuOK or ^<i>t</i>BuONa) mediated generation of aryl free radical from aryl iodide remarks a milestone discovery in the free radical chemistry. However, the equivalent “alkyl halide to alkyl free radical” transformation has not yet been realized in applicable synthesis by similar catalytic tactic. In this paper, the first practical “alkyl halide to alkyl free radical” transformation mediated by ^<i>t</i>BuOK or TMSOK in the direct α-C—H alkylation of benzoins is presented. As the parallelly significant issue as aryl free radical generation, the current work, while bringing a rather facile and useful new approach for the synthesis of diverse benzoins, represents also an important step in the alkyl free radical-based synthesis by displaying the higher generality of simple alkali base mediated radical formation.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"42 23","pages":"3041-3046"},"PeriodicalIF":5.5,"publicationDate":"2024-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141871807","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":"Stimuli-Responsive Interconversion between Poly-NHC-Based Organometallic Assemblies and Their Self-Aggregated Dimers","authors":"Guang-Feng Jin,&nbsp;Ying-Feng Han","doi":"10.1002/cjoc.202400501","DOIUrl":"10.1002/cjoc.202400501","url":null,"abstract":"<div>\u0000 \u0000 <p>Poly-NHC-based organometallic assemblies <b>3-PF</b>_<b>6</b><b>, 3-SbF</b>_<b>6</b> and <b>3-OTf</b> were obtained and verified by NMR spectroscopy, ESI mass spectrometry and single-crystal X-ray diffraction analyses. Controllable structural interconversion was observed between the poly-NHC-based organometallic assemblies and their self-aggregated dimers in solution affected by concentration, solvent and metal ion. ¹H NMR spectra of assembly <b>3-PF</b>_<b>6</b> in CD₃CN at different concentrations demonstrated controllable structural interconversion, and ¹⁹F NMR spectrum of assembly <b>3-PF</b>_<b>6</b> at high concentration further evidenced the presence of the free hexafluorophosphate anion and encapsulated hexafluorophosphate anion for its two sets of signals. In addition, single-crystal X-ray diffraction analysis provided clear evidence that in the solid state, two assemblies <b>3-PF</b>_<b>6</b> were vertically stuck, forming a self-aggregated dimer with an encapsulated hexafluorophosphate anion. Investigating the reversible structural interconversion is beneficial for revealing the intrinsic nature on the atom level and paving the way to design the stimuli-responsive functional system.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"42 22","pages":"2840-2844"},"PeriodicalIF":5.5,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141754049","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":"Substituent Modulated Electronic Properties of Cu(I) Active Site in Metal–Organic Halides for Boosting Hydrogen Evolution Reaction†","authors":"Jing Wu,&nbsp;Pingping Wang,&nbsp;Yuzhe Fu,&nbsp;Yi Shen,&nbsp;Bin Wang,&nbsp;Feng Hu,&nbsp;Mengkai Zuo,&nbsp;Wei Huang,&nbsp;Dayu Wu","doi":"10.1002/cjoc.202400514","DOIUrl":"10.1002/cjoc.202400514","url":null,"abstract":"<div>\u0000 \u0000 <p>Development of heterogeneous molecular photocatalysts for promising light-driven hydrogen evolution reaction (HER) is highly demanding but still challenging. Here, we report the blue-greenish emitting dinuclear metal–organic halides as photocatalyst by incorporating site-specific single copper(I) atoms that exhibit an efficient carbon-negative H₂ production. Interestingly, the electronic properties, including the spin and charge density of central Cu(I) active site, can be triggered by substituent modulation in metal–organic halides, which greatly affect the exciton dissociation kinetics and thus the HER reactivity. The optimized spin density in these heterogeneous photocatalysts drastically boosts the hydrogen production rate from 1250 to 3130 μmol·g^–1·h^–1. Our molecular strategy provides a platform that rationally facilitates electronic modulation of copper(I) atoms, tunes the macroscopic optoelectronic properties of photocatalysts and boosts carbon-negative HER activity, extending the boundaries of conventional molecular-based photocatalysts.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"42 22","pages":"2845-2852"},"PeriodicalIF":5.5,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141754089","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":"Enantioselective Total Synthesis of (+)-Propolisbenzofuran B†","authors":"Wen-Xiu Xu,&nbsp;Li-Han Zhao,&nbsp;Yao Zhu,&nbsp;Hai-Hua Lu","doi":"10.1002/cjoc.202400563","DOIUrl":"10.1002/cjoc.202400563","url":null,"abstract":"<div>\u0000 \u0000 <p>The first catalytic asymmetric total synthesis of (+)-propolisbenzofuran B, enabled by a highly enantioselective rhodium-catalyzed hydrogenation of a tetrasubstituted olefin, was described. Other noteworthy aspects include the construction of the central hydrodibenzo[<i>b</i>,<i>d</i>]furan core through a sequence of Zn(II)-mediated regioselective benzofuran formation and Dieckmann condensation, as well as C-H oxidations, involving a visible light-induced Fe(III)-catalyzed benzylic C(sp³)-H oxidation. Additionally, the absolute configuration was confirmed by X-ray analysis of a carbonate intermediate.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"42 22","pages":"2833-2839"},"PeriodicalIF":5.5,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141786307","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":"Recent Advances of Amorphous Nanomaterials: Synthesis and Applications","authors":"Lidong Li,&nbsp;Hewei Zhao,&nbsp;Xiaotian Wang,&nbsp;Lin Guo","doi":"10.1002/cjoc.202400388","DOIUrl":"10.1002/cjoc.202400388","url":null,"abstract":"&lt;div&gt;\u0000 \u0000 &lt;section&gt;\u0000 \u0000 &lt;h3&gt; Comprehensive Summary&lt;/h3&gt;\u0000 \u0000 &lt;p&gt;Amorphous nanomaterials are metastable nanomaterials which only have short-range order within a few neighboring atoms, based on the local chemical bondings. Different from crystalline materials, the amorphous nanomaterials lack of long-range order exhibit many intriguing and unique structu ral features, such as abundant active sites, structural flexibility, intrinsic isotropy and fast ionic transport. However, due to the unco nventional structural complexity, the systematic study and understanding of amorphous nanomaterials are still in the early stage. In this review, we will describe our journey to the synthesis, characterization and applications of amorphous nanomaterials, including catalysis, energy storage, optics and mechanics.&lt;/p&gt;\u0000 \u0000 &lt;p&gt;&lt;/p&gt;\u0000 \u0000 &lt;p&gt;&lt;b&gt;&lt;i&gt;What is the most favorite and original chemistry developed in your research group?&lt;/i&gt;&lt;/b&gt;&lt;/p&gt;\u0000 \u0000 &lt;p&gt;Our group developed a variety of universal methods, such as \"coordination etching\" method, \"self-hydrolytic etch-precipitation\" method, photoetching method, co-precipitation method, &lt;i&gt;etc&lt;/i&gt;., to achieve the controllable preparation of amorphous nanomaterials with different morphology, size and dimension, and the catalytic, mechanical and optical properties of the materials and their potential applications were also studied. Moreover, the relevant mechanisms were proposed, the structure-activity relationship was established, and the development and application of amorphous micro-nanomaterials were promoted.&lt;/p&gt;\u0000 \u0000 &lt;p&gt;&lt;b&gt;&lt;i&gt;How do you get into this specific field? Could you please share some experiences with our readers?&lt;/i&gt;&lt;/b&gt;&lt;/p&gt;\u0000 \u0000 &lt;p&gt;My journey into the field of amorphous nanomaterials began 20 years ago when I developed a fascination for materials science and nanotechnology. During my early research experiences, I encountered the intriguing world of amorphous nanomaterials. These materials, lacking a long-range crystalline order, presented both challenges and opportunities in terms of their synthesis and understanding their properties. It's a field where creativity and precision intersect, driving me to continually seek innovative solutions and deepen my understanding of nanoscale phenomena.&lt;/p&gt;\u0000 \u0000 &lt;p&gt;&lt;b&gt;&lt;i&gt;How do you supervise your students?&lt;/i&gt;&lt;/b&gt;&lt;/p&gt;\u0000 \u0000 &lt;p&gt;As a professor, I supervise students by setting clear expectations, holding regular meetings for feedback and guidance, and encouraging&lt;/p&gt;\u0000 \u0000 &lt;p&gt;independent thinking. I support their career development by identifying opportunities and creating a collaborative environment. Adapting to individual needs, I foster a fair and consistent approach to help students grow professionally and academically.&lt;/p&gt;\u0000 \u0000 &lt;p&gt;&lt;b&gt;&lt;i&gt;What ","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"42 22","pages":"2853-2876"},"PeriodicalIF":5.5,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141784222","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":"In-situ Post-Synthetic Treatment of CsPbBr3 Perovskite Nanocrystals in Nanoporous Silica Microspheres","authors":"Danila A. Tatarinov,&nbsp;Jinfeng Xie,&nbsp;Qingyi Qian,&nbsp;Qingqing Wang,&nbsp;Nadezhda A. Maslova,&nbsp;Lyubov N. Borodina,&nbsp;Aleksandr P. Litvin,&nbsp;He Huang","doi":"10.1002/cjoc.202400513","DOIUrl":"10.1002/cjoc.202400513","url":null,"abstract":"<div>\u0000 \u0000 <p>Inorganic lead halide perovskite (LHP) nanostructures, represented by formula CsPbX₃ (X = Cl, Br, I), have garnered considerable interest for their exceptional optical properties and diverse applications. Despite their potential, challenges such as environmental degradation persist. <i>In-situ</i> synthesis within protective materials pores is a promising way to address this issue. However, confining perovskite nanostructures into porous matrices during the synthesis can limit their photoluminescence quantum yield (PL QY) and tunability of optical properties. Various post-treatment approaches exist to improve the properties of LHP and achieve their desired functionalities, but these strategies have not been explored for LHP confined in mesoporous matrices. Here, we demonstrate the efficacy of <i>in-situ</i> post-synthetic treatments to improve the optical properties of CsPbBr₃ nanocrystals grown in nanoporous silica microspheres. Surface passivation with Br^– ion-containing precursors boosts PL QY, while anion-assisted cation doping with Mn²⁺ ions introduces a new PL band. The adjustment of precursor amount and doping duration enables precise control over the optical properties of LHP, while additional coating with a SiO₂ shell enhances their stability in polar solvents, expanding the potential applications of these composites.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"42 22","pages":"2779-2787"},"PeriodicalIF":5.5,"publicationDate":"2024-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141737501","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":"Co-Catalyzed Dehydrogenation Claisen Condensation of Secondary Alcohols with Esters†","authors":"Shuo Gao,&nbsp;Wentao Hao,&nbsp;Yuqi Ji,&nbsp;Xiulin Li,&nbsp;Chunyan Zhang,&nbsp;Guoying Zhang","doi":"10.1002/cjoc.202400481","DOIUrl":"10.1002/cjoc.202400481","url":null,"abstract":"<div>\u0000 \u0000 <p>Catalytic dehydrogenation, with its exceptional atom economy and chemoselectivity, offers a highly desirable yet challenging approach for converting multiple environmentally friendly alcohols into crucial molecules. Furthermore, the utilization of catalysts based on abundant elements found on Earth for alcohol dehydrogenation to produce acryl ketone holds significant promise as a versatile strategy in synthesizing key building blocks for numerous pharmaceutical applications. The present study describes a practical Co-catalyzed cascade dehydrogenative Claisen condensation of secondary alcohols with esters, facilitating the synthesis of a wide range of 3-hydroxy-prop-2-en-1-ones. We introduce a catalytic system based on novel and scalable indazole NNP-ligands coordinated to cobalt for efficient dehydrogenations of secondary alcohols, and propose a plausible reaction mechanism supported by control experiments and labeling studies. Notably, it allows for the streamlined synthesis of multiple pharmaceuticals in one-pot.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"42 22","pages":"2818-2824"},"PeriodicalIF":5.5,"publicationDate":"2024-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141737503","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":"On-surface Synthesis of Multiple Non-benzenoid Carbohelicenes Fused with Fluorene Unit(s)","authors":"Wei Xiong,&nbsp;Xi Geng,&nbsp;Jianchen Lu,&nbsp;Gefei Niu,&nbsp;Boyu Fu,&nbsp;Yi Zhang,&nbsp;Shicheng Li,&nbsp;Yuhang Yang,&nbsp;Nianqiang Li,&nbsp;Lei Gao,&nbsp;Jinming Cai","doi":"10.1002/cjoc.202400341","DOIUrl":"10.1002/cjoc.202400341","url":null,"abstract":"<div>\u0000 \u0000 <p>Carbohelicenes have garnered considerable attention for their inherent chirality and structural flexibility. Increasing multi-helicity and incorporating non-six-membered rings to substitute benzenoid rings within helicenes are effective strategies for introducing unique photoelectric properties. Despite the disclosure of numerous helicenes, the inaccessible precursors and the lack of synthetic routes pose a challenge in achieving desired helicene structures fused with non-benzenoid rings. Herein, we report the synthesis of multiple non-benzenoid carbohelicenes fused with fluorene unit(s) through intramolecular cyclodehydrogenation of 9,10-di(naphthalen-1- yl)anthracene on Au(111) surface. Two potential cyclodehydrogenation manners between naphthyl and anthracene lead to the formation of fluorene-fused [5]helicene and [4]helicene moiety. Consequently, a total of four stable products were observed. The atomic topographies of products are characterized by bond-resolving scanning tunneling microscopy. The chiral helicity of targeted products can be switched by tip manipulation. Density-functional-theory calculations unveils the reaction pathway of four products. The comparative analysis of their respective energy barriers exhibits a correlation with the experimentally determined yields. Furthermore, we synthesize the polymer chains incorporating non-benzenoid carbohelicenes <i>via</i> the Ullmann reaction of 2,6-dibromo-9,10-di(1-naphthyl)anthracene precursors. Our work proposes a synthetic methodology for several novel helicene-like structures fused with fluorene units and the polymer bearing helicene subunits, thus highlighting the immense potential of these compounds in the application fields of luminescent electronic devices.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"42 22","pages":"2811-2817"},"PeriodicalIF":5.5,"publicationDate":"2024-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141737504","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":"Functionalization of Boranes through Thiol/Oxygen Catalysis†","authors":"Hongyi Tao,&nbsp;Hairong Lyu","doi":"10.1002/cjoc.202400494","DOIUrl":"10.1002/cjoc.202400494","url":null,"abstract":"<p>A greener and more convenient alternative to traditional methods for the generation of thiyl radical as hydrogen atom transfer (HAT) catalyst is developed, using molecular oxygen to oxidize thiol without the need for chemical initiators or light irradiation. The thiol/oxygen catalysis enables selective and efficient difunctionalization of borane.</p><p>\u0000 </p>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"42 22","pages":"2804-2810"},"PeriodicalIF":5.5,"publicationDate":"2024-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cjoc.202400494","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141737502","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":"Secondary Aggregation Induced by Volatile Additive for Improved Exciton Diffusion and Charge Separation in High Efficiency Organic Photovoltaic Devices","authors":"Yufeng Ge,&nbsp;Xuewu Li,&nbsp;Mingxu Zhou,&nbsp;Peng Lu,&nbsp;Xiaotao Hao","doi":"10.1002/cjoc.202400397","DOIUrl":"10.1002/cjoc.202400397","url":null,"abstract":"<div>\u0000 \u0000 <p>The morphology of the active layer plays a crucial role in the performance of organic photovoltaics. Although volatile additives are commonly used to manipulate the morphology, their mechanism of action remains poorly understood. In this study, we conducted a systematic exploration of the mechanism of the traditional volatile additive 1-CN in film formation kinetics of typical PM6:Y6 system. We found that 1-CN induces a secondary aggregation effect, improving film morphology and promoting face-on crystalline orientation. Through elucidating its impact on exciton dynamics, we established a link between morphology optimization and increased exciton diffusion length and accelerated charge separation. Our findings unveil the unique mechanism of action of volatile additive, providing a new perspective for improving the morphology and enhancing the performance of organic photovoltaic devices.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"42 22","pages":"2825-2832"},"PeriodicalIF":5.5,"publicationDate":"2024-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141737505","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}