Wiktoria Adamowicz, Dr. Kasidid Yaemsunthorn, Dr. Marcin Kobielusz, Prof. Wojciech Macyk
The front cover article describes the recent progress in the field of photocatalytic transformation of organics to valuable chemicals. This comprehensive review highlights how photocatalysis can be involved in selective transformations of organic compounds, including reduction and coupling reactions such as C-C and C-N couplings. By examining intrinsic and extrinsic factors, the authors provide insights into the rational design of efficient and stable photocatalytic systems dedicated to the synthesis of fine chemicals. More details can be found in the Review by Marcin Kobielusz, Wojciech Macyk, and co-workers (DOI: 10.1002/cplu.202400171).
封面文章介绍了光催化将有机物转化为有价值化学品领域的最新进展。这篇综述重点介绍了光催化如何参与有机化合物的选择性转化，包括还原和偶联反应，如 C-C 和 C-N 偶联。通过研究内在和外在因素，作者深入探讨了如何合理设计专用于精细化学品合成的高效、稳定的光催化系统。更多详情，请参阅 Marcin Kobielusz、Wojciech Macyk 及合作者的评论文章（DOI: 10.1002/cplu.202400171）。
{"title":"Front Cover: Photocatalytic Transformation of Organics to Valuable Chemicals – Quo Vadis? (ChemPlusChem 9/2024)","authors":"Wiktoria Adamowicz, Dr. Kasidid Yaemsunthorn, Dr. Marcin Kobielusz, Prof. Wojciech Macyk","doi":"10.1002/cplu.202480901","DOIUrl":"https://doi.org/10.1002/cplu.202480901","url":null,"abstract":"<p><b>The front cover article</b> describes the recent progress in the field of photocatalytic transformation of organics to valuable chemicals. This comprehensive review highlights how photocatalysis can be involved in selective transformations of organic compounds, including reduction and coupling reactions such as C-C and C-N couplings. By examining intrinsic and extrinsic factors, the authors provide insights into the rational design of efficient and stable photocatalytic systems dedicated to the synthesis of fine chemicals. More details can be found in the Review by Marcin Kobielusz, Wojciech Macyk, and co-workers (DOI: 10.1002/cplu.202400171).<figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"89 9","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cplu.202480901","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142231100","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Miquel Cardona-Farreny, Hiroya Ishikawa, Abolanle Olatilewa Odufejo Ogoe, Sonia Mallet-Ladeira, Yannick Coppel, Pierre Lecante, Jerome Esvan, Karine Philippot, M. Rosa Axet
Colloidal metal nanoparticles exhibit interesting catalytic properties for the hydrogenation of (hetero)arenes. Catalysts based on precious metals, such as Ru and Rh, proceed efficiently under mild reaction conditions. In contrast, heterogeneous catalysts based on earth‐abundant metals can selectively hydrogenate (hetero)arenes but require harsher reaction conditions. Bimetallic catalysts that combine precious and earth‐abundant metals are interesting materials to mitigate the drawbacks of each component. To this end, RuNi nanoparticles bearing a phosphine ligand were prepared through the decomposition of [Ru(η4‐C8H12)(η6‐C8H10)] and [Ni(η4‐C8H12)2] by H2 at 85°C. Wide angle X‐ray scattering confirmed a bimetallic segregated structure, with Ni predominantly on the surface. Spectroscopic analyses revealed that the phosphine ligand coordinated to the surface of both metals, suggesting, as well, a partial Ni shell covering the Ru core. The RuNi‐based nanomaterials were used as catalysts in the hydrogenation of quinoline to assess the impact of the metallic composition and of the stabilizing agent on their catalytic performance.
胶体金属纳米粒子在（杂）炔的氢化反应中表现出有趣的催化特性。基于贵金属（如 Ru 和 Rh）的催化剂可在温和的反应条件下高效地进行反应。相比之下，基于富土金属的异相催化剂可以选择性地氢化（杂）炔，但需要更苛刻的反应条件。结合了贵金属和富土金属的双金属催化剂是一种有趣的材料，可以减轻每种成分的缺点。为此，我们在 85°C 下通过 H2 分解[Ru(η4-C8H12)(η6-C8H10)]和[Ni(η4-C8H12)2]制备了带有膦配体的 RuNi 纳米粒子。广角 X 射线散射证实了双金属偏析结构，镍主要位于表面。光谱分析显示，膦配体同时配位在两种金属的表面，这也表明在 Ru 内核上有部分 Ni 外壳。RuNi 基纳米材料被用作喹啉氢化的催化剂，以评估金属成分和稳定剂对其催化性能的影响。
{"title":"Colloidal Bimetallic RuNi Particles and their Behaviour in Catalytic Quinoline Hydrogenation","authors":"Miquel Cardona-Farreny, Hiroya Ishikawa, Abolanle Olatilewa Odufejo Ogoe, Sonia Mallet-Ladeira, Yannick Coppel, Pierre Lecante, Jerome Esvan, Karine Philippot, M. Rosa Axet","doi":"10.1002/cplu.202400516","DOIUrl":"https://doi.org/10.1002/cplu.202400516","url":null,"abstract":"Colloidal metal nanoparticles exhibit interesting catalytic properties for the hydrogenation of (hetero)arenes. Catalysts based on precious metals, such as Ru and Rh, proceed efficiently under mild reaction conditions. In contrast, heterogeneous catalysts based on earth‐abundant metals can selectively hydrogenate (hetero)arenes but require harsher reaction conditions. Bimetallic catalysts that combine precious and earth‐abundant metals are interesting materials to mitigate the drawbacks of each component. To this end, RuNi nanoparticles bearing a phosphine ligand were prepared through the decomposition of [Ru(η4‐C8H12)(η6‐C8H10)] and [Ni(η4‐C8H12)2] by H2 at 85°C. Wide angle X‐ray scattering confirmed a bimetallic segregated structure, with Ni predominantly on the surface. Spectroscopic analyses revealed that the phosphine ligand coordinated to the surface of both metals, suggesting, as well, a partial Ni shell covering the Ru core. The RuNi‐based nanomaterials were used as catalysts in the hydrogenation of quinoline to assess the impact of the metallic composition and of the stabilizing agent on their catalytic performance.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"7 1","pages":""},"PeriodicalIF":3.4,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142255871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wenkang Jin, Dr. Masanori Nagao, Yusuke Kumon, Dr. Hikaru Matsumoto, Prof. Yu Hoshino, Prof. Yoshiko Miura
The cover feature shows how the cyclization of the polymer main chain suppresses the molecular mobility of the glycopolymers. This suppression of mobility is expected to enhance biomolecular interactions by avoiding entropy loss in the polymer conformation. More details can be found in the Research Article by Masanori Nagao, Yoshiko Miura, and co-workers (DOI: 10.1002/cplu.202400136).
{"title":"Effects of Cyclic Glycopolymers Molecular Mobility on their Interactions with Lectins","authors":"Wenkang Jin, Dr. Masanori Nagao, Yusuke Kumon, Dr. Hikaru Matsumoto, Prof. Yu Hoshino, Prof. Yoshiko Miura","doi":"10.1002/cplu.202480902","DOIUrl":"https://doi.org/10.1002/cplu.202480902","url":null,"abstract":"<p><b>The cover feature shows</b> how the cyclization of the polymer main chain suppresses the molecular mobility of the glycopolymers. This suppression of mobility is expected to enhance biomolecular interactions by avoiding entropy loss in the polymer conformation. More details can be found in the Research Article by Masanori Nagao, Yoshiko Miura, and co-workers (DOI: 10.1002/cplu.202400136).<figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"89 9","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cplu.202480902","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142231108","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kseniya V. Arsenyeva, Anastasiya V. Klimashevskaya, Arina.V. Владимирович Maleeva, Maxim V. Arsenyev, Maxim G. Chegerev, Alyona A. Starikova, Ilya A. Yakushev, Anton V. Cherkasov, Alexandr Vladimirovich Piskunov
Synthesis and structural characterization of a family of germanium‐dioxolene complexes with ditopic N‐donor ligands (L1‐L5) (L1 = 1,2‐bis(pyridin‐2‐ylmethylene)hydrazine L2 = 1,6‐bis‐(pyridin‐2‐yl)‐2,5‐diaza‐1,5‐heхаdiene, L3 = N,N‐bis(pyridin‐2‐ylmethylene)‐1,4‐benzenediamine, L4 = N,N‐bis(pyridin‐2‐ylmethylene)‐(biphenyl)‐4,4‐diamine, L5 = 2,2’‐azopyridine) is reported. The reaction of germanium bis‐catecholate with bridging ligands L1 – L4, differing by the nature of the linker between pyridine sites gives rise to dinuclear digermanium complexes (36Cat2Ge)2L1‐4 (36Cat = dianion of 3,6‐di‐tert‐butylcatechol) 1‐4 of DMAMD type (donor‐metal‐acceptor‐metal‐donor) with a charge transfer in the UV‐Vis region. In opposite, the interaction of the 36Cat2Ge with 2,2’‐azopyridine (L5) results in the two‐electron transfer from the donor 36Cat2‐ ligands to the azopyridine bridge forming stable open‐shell complex 5 [(36SQ)(36CatGe)]2(L5)2‐ (36SQ = radical‐anionic semiquinonate ligand). Molecular structures of compounds 3 and 5 were determined by single crystal X‐ray diffraction analysis. Electronic structures of complexes 1‐5 were studied by means of DFT calculations.
{"title":"Bridge‐dependent donor‐metal‐acceptor‐metal‐donor (D‐M‐A‐M‐D) systems: from charge transfer to electron transfer in dioxolene‐Ge‐diimine complexes.","authors":"Kseniya V. Arsenyeva, Anastasiya V. Klimashevskaya, Arina.V. Владимирович Maleeva, Maxim V. Arsenyev, Maxim G. Chegerev, Alyona A. Starikova, Ilya A. Yakushev, Anton V. Cherkasov, Alexandr Vladimirovich Piskunov","doi":"10.1002/cplu.202400504","DOIUrl":"https://doi.org/10.1002/cplu.202400504","url":null,"abstract":"Synthesis and structural characterization of a family of germanium‐dioxolene complexes with ditopic N‐donor ligands (L1‐L5) (L1 = 1,2‐bis(pyridin‐2‐ylmethylene)hydrazine L2 = 1,6‐bis‐(pyridin‐2‐yl)‐2,5‐diaza‐1,5‐heхаdiene, L3 = N,N‐bis(pyridin‐2‐ylmethylene)‐1,4‐benzenediamine, L4 = N,N‐bis(pyridin‐2‐ylmethylene)‐(biphenyl)‐4,4‐diamine, L5 = 2,2’‐azopyridine) is reported. The reaction of germanium bis‐catecholate with bridging ligands L1 – L4, differing by the nature of the linker between pyridine sites gives rise to dinuclear digermanium complexes (36Cat2Ge)2L1‐4 (36Cat = dianion of 3,6‐di‐tert‐butylcatechol) 1‐4 of DMAMD type (donor‐metal‐acceptor‐metal‐donor) with a charge transfer in the UV‐Vis region. In opposite, the interaction of the 36Cat2Ge with 2,2’‐azopyridine (L5) results in the two‐electron transfer from the donor 36Cat2‐ ligands to the azopyridine bridge forming stable open‐shell complex 5 [(36SQ)(36CatGe)]2(L5)2‐ (36SQ = radical‐anionic semiquinonate ligand). Molecular structures of compounds 3 and 5 were determined by single crystal X‐ray diffraction analysis. Electronic structures of complexes 1‐5 were studied by means of DFT calculations.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"27 1","pages":""},"PeriodicalIF":3.4,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142255840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tatiana E. Kokina, Nikita A. Shekhovtsov, Alexey V. Tkachev, Alexander M. Agafontsev, Christophe Gourlaouen, Mark B. Bushuev
The first example of the palladium‐catalyzed sp3 C‐H bond activation in a monoterpene‐based compound has been observed in the reaction of PdCl2 with a (+)‐3‐carene‐based ligand HL (HL = N‐((1aS,3S,7bR)‐1,1,3‐trimethyl‐7‐phenyl‐5‐(pyridin‐2‐yl)‐1a,2,3,7b‐tetrahydro‐1H‐cyclopropa[f]quinolin‐3‐yl)acetamide), which yielded the [PdLCl] complex. In contrast to the vast majority of C(sp3)‐H activation reactions which require prolonged heating and mixing due to the inert character of the corresponding bond, the reaction reported herein proceeds rapidly under mild conditions. A theoretical insight into the ligand deprotonation has been performed by DFT calculations. The mechanism of the C‐H activation involves (i) simultaneous coordination of the CH3 group of HL to the Pd2+ ion and decoordination of the Cl‐ anion with consequent formation of a Cl⋅⋅⋅H‐N hydrogen bond with the amide group, (ii) approximation of the out‐of‐sphere Cl‐ anion to one of the hydrogen atoms of the CH3 group mediated by the crane motion of the amide group and (iii) the ejection of the HCl molecule, which increases the entropy of the system and serves as a driving force for the reaction.
{"title":"Palladium‐catalyzed C(sp3)‐H activation in a monoterpene‐based compound under mild conditions: a combined experimental and theoretical mechanistic study","authors":"Tatiana E. Kokina, Nikita A. Shekhovtsov, Alexey V. Tkachev, Alexander M. Agafontsev, Christophe Gourlaouen, Mark B. Bushuev","doi":"10.1002/cplu.202400509","DOIUrl":"https://doi.org/10.1002/cplu.202400509","url":null,"abstract":"The first example of the palladium‐catalyzed sp3 C‐H bond activation in a monoterpene‐based compound has been observed in the reaction of PdCl2 with a (+)‐3‐carene‐based ligand HL (HL = N‐((1aS,3S,7bR)‐1,1,3‐trimethyl‐7‐phenyl‐5‐(pyridin‐2‐yl)‐1a,2,3,7b‐tetrahydro‐1H‐cyclopropa[f]quinolin‐3‐yl)acetamide), which yielded the [PdLCl] complex. In contrast to the vast majority of C(sp3)‐H activation reactions which require prolonged heating and mixing due to the inert character of the corresponding bond, the reaction reported herein proceeds rapidly under mild conditions. A theoretical insight into the ligand deprotonation has been performed by DFT calculations. The mechanism of the C‐H activation involves (i) simultaneous coordination of the CH3 group of HL to the Pd2+ ion and decoordination of the Cl‐ anion with consequent formation of a Cl⋅⋅⋅H‐N hydrogen bond with the amide group, (ii) approximation of the out‐of‐sphere Cl‐ anion to one of the hydrogen atoms of the CH3 group mediated by the crane motion of the amide group and (iii) the ejection of the HCl molecule, which increases the entropy of the system and serves as a driving force for the reaction.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"117 1","pages":""},"PeriodicalIF":3.4,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142255839","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rui Zhang, Dandan Luo, Mohammad Jaber, Han ZHANG, Xiangdong Kong
The antibacterial properties of modified silk fibroin microfibers (SF MFs) have been widely studied. Among various modifications, integration of silver nanoparticles (Ag NPs) and SF MFs has garnered significant attention due to the broad‐spectrum antibacterial activities and long‐term antibacterial effect of Ag nanomaterials. However, the traditional introduction of reducing agents or other additives during the synthesis of Ag‐SF composite MFs potentially affects their structure and antibacterial properties. Facile, green and effective methods for the preparation of Ag‐SF MFs with enhanced antibacterial properties are therefore highly desired. In this study, Ag NPs were uniformly in‐situ deposited onto the optimized SF MFs by adjusting the pH and duration conditions under the guidance of green chemistry. The loaded Ag NPs have a good dispersibility and an average size of ~10 nm. The stability of SF MFs after the deposition of Ag NPs and the crystalline features of the loaded Ag NPs have been carefully investigated. Moreover, antibacterial experiments confirmed that Ag‐SF MFs exhibited superior antibacterial activities. After co‐incubating Ag‐SF MFs with L929 cells, the cell viability reached 90%, demonstrating the great biocompatibility of the modified fibers. This green in‐situ synthetic method will promote the further medical use of Ag‐SF MFs in antibacterial fields.
改性蚕丝纤维（SF MFs）的抗菌特性已被广泛研究。在各种改性中，银纳米粒子（Ag NPs）与蚕丝复合纤维的结合引起了广泛关注，因为银纳米材料具有广谱抗菌活性和长期抗菌效果。然而，在合成 Ag-SF 复合 MFs 的过程中，传统的还原剂或其他添加剂的引入可能会影响其结构和抗菌性能。因此，制备具有更强抗菌性能的 Ag-SF MFs 的简便、绿色和有效方法备受青睐。本研究在绿色化学的指导下，通过调节 pH 值和时间条件，将 Ag NPs 均匀地原位沉积到优化的 SF MFs 上。负载的 Ag NPs 具有良好的分散性，平均尺寸约为 10 nm。研究人员仔细考察了沉积 Ag NPs 后 SF MF 的稳定性和负载 Ag NPs 的结晶特征。此外，抗菌实验证实，Ag-SF MFs 具有优异的抗菌活性。将 Ag-SF MFs 与 L929 细胞共培养后，细胞存活率达到 90%，表明改性纤维具有良好的生物相容性。这种绿色原位合成方法将促进 Ag-SF MFs 在抗菌领域的进一步医疗应用。
{"title":"In‐Situ and Green Synthesis of Silk Fibroin‐Silver Nanoparticles Composite Microfibers for Enhanced Antibacterial Applications","authors":"Rui Zhang, Dandan Luo, Mohammad Jaber, Han ZHANG, Xiangdong Kong","doi":"10.1002/cplu.202400478","DOIUrl":"https://doi.org/10.1002/cplu.202400478","url":null,"abstract":"The antibacterial properties of modified silk fibroin microfibers (SF MFs) have been widely studied. Among various modifications, integration of silver nanoparticles (Ag NPs) and SF MFs has garnered significant attention due to the broad‐spectrum antibacterial activities and long‐term antibacterial effect of Ag nanomaterials. However, the traditional introduction of reducing agents or other additives during the synthesis of Ag‐SF composite MFs potentially affects their structure and antibacterial properties. Facile, green and effective methods for the preparation of Ag‐SF MFs with enhanced antibacterial properties are therefore highly desired. In this study, Ag NPs were uniformly in‐situ deposited onto the optimized SF MFs by adjusting the pH and duration conditions under the guidance of green chemistry. The loaded Ag NPs have a good dispersibility and an average size of ~10 nm. The stability of SF MFs after the deposition of Ag NPs and the crystalline features of the loaded Ag NPs have been carefully investigated. Moreover, antibacterial experiments confirmed that Ag‐SF MFs exhibited superior antibacterial activities. After co‐incubating Ag‐SF MFs with L929 cells, the cell viability reached 90%, demonstrating the great biocompatibility of the modified fibers. This green in‐situ synthetic method will promote the further medical use of Ag‐SF MFs in antibacterial fields.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"27 1","pages":"e202400478"},"PeriodicalIF":3.4,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kirill P. Birin, Daria A. Polivanovskaia, Inna A. Abdulaeva, Yulia G. Gorbunova, Aslan Yu. Tsivadze
An exceptional efficiency of pyrazine‐annelated porphyrin as a general photocatalyst for the oxidation of organic sulfides is demonstrated. It is shown that phosphonate‐substituted pyrazinoporphyrin 2H‐1 brings together sufficient photostability and high efficiency in the aerobic photooxidation of a series of various sulfides. The influence of the reaction conditions onto the efficiency of homogeneous sulfide photooxidation in the presence of the PS was investigated and strong dependence on the solvent system was observed. The use of methanol is required for the photocatalytic sulfoxidation and the ratio of the alcohol/other solvent can significantly affect the conversion and selectivity of the reaction. The application of the prepared photosensitizer (PS) in 0.001 mol% loading allowed achieving complete conversion (97‐100%, turnover number up to 100000, turnover frequency up to 6250 h‐1) of substrates bearing substituents of different nature, namely aromatic and aliphatic sulfides with donor or acceptor substituents and substituents prone to oxidation, as well as cyclic sulfides. The selectivity of the of the corresponding sulfoxides formation of 96‐100% was revealed. Finally, a gram‐scale synthesis of several sulfoxides was successfully performed with the PS under investigation, providing desired products in 66‐96% yield with over 98% purity.
{"title":"Phosphonate‐substituted Pyrazinoporphyrin – a General Photocatalyst for Efficient Sulfoxidation","authors":"Kirill P. Birin, Daria A. Polivanovskaia, Inna A. Abdulaeva, Yulia G. Gorbunova, Aslan Yu. Tsivadze","doi":"10.1002/cplu.202400469","DOIUrl":"https://doi.org/10.1002/cplu.202400469","url":null,"abstract":"An exceptional efficiency of pyrazine‐annelated porphyrin as a general photocatalyst for the oxidation of organic sulfides is demonstrated. It is shown that phosphonate‐substituted pyrazinoporphyrin 2H‐1 brings together sufficient photostability and high efficiency in the aerobic photooxidation of a series of various sulfides. The influence of the reaction conditions onto the efficiency of homogeneous sulfide photooxidation in the presence of the PS was investigated and strong dependence on the solvent system was observed. The use of methanol is required for the photocatalytic sulfoxidation and the ratio of the alcohol/other solvent can significantly affect the conversion and selectivity of the reaction. The application of the prepared photosensitizer (PS) in 0.001 mol% loading allowed achieving complete conversion (97‐100%, turnover number up to 100000, turnover frequency up to 6250 h‐1) of substrates bearing substituents of different nature, namely aromatic and aliphatic sulfides with donor or acceptor substituents and substituents prone to oxidation, as well as cyclic sulfides. The selectivity of the of the corresponding sulfoxides formation of 96‐100% was revealed. Finally, a gram‐scale synthesis of several sulfoxides was successfully performed with the PS under investigation, providing desired products in 66‐96% yield with over 98% purity.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"22 1","pages":""},"PeriodicalIF":3.4,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We present the synthesis, structural characterization, and reactivity studies of a tetra‐zinc complex supported by the bisphenoxymethanone ligands and its transformation into various di‐zinc architectures. Our findings highlight the potential of these complexes in molecular recognition, supramolecular chemistry, and catalysis.
{"title":"Coordination Chemistry and Reactivity of a Lewis Acidic Di‐Zinc Framework Supported by Bisphenoxymethanone Ligands","authors":"Ding-Hong Wu, Xin-Jie Lin, Wachara Benchaphanthawee, Yen-Hua Lee, Zih-Chen Lin, Han-Jung Li, Pei-Lin Chen, Ting-Shen Kuo, Chien-Lung Wang, Yen-Ku Wu, Chi-How Peng, Hsueh-Ju Liu","doi":"10.1002/cplu.202400382","DOIUrl":"https://doi.org/10.1002/cplu.202400382","url":null,"abstract":"We present the synthesis, structural characterization, and reactivity studies of a tetra‐zinc complex supported by the bisphenoxymethanone ligands and its transformation into various di‐zinc architectures. Our findings highlight the potential of these complexes in molecular recognition, supramolecular chemistry, and catalysis.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"77 1","pages":""},"PeriodicalIF":3.4,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207307","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Desolvation processes, though common in self-assembled biological structures, are rarely evidenced and utilized in the design of crystalline architectures. In this study, we introduce a novel approach using the [Mo8S8O8(OH)8(guest)]2- complex, formed by the self-condensation of four [MoV2O2S2]2- fragments around a guest unit (MoVIO6H4 or oxalate), as a chaotropic scaffold for crystallizing hybrid organic-inorganic systems with natural cyclodextrins. Our findings reveal that β-cyclodextrin (β-CD) facilitates the formation of host-guest complexes, while α-cyclodextrin (α-CD) induces the formation of a Kagome-type structure with significant voids. These new compounds were thoroughly characterized using X-ray diffraction (both powder and single-crystal), N2 adsorption, elemental and thermogravimetric analysis. Additionally, solution studies using 1H NMR titration and small-angle X-ray scattering (SAXS) demonstrated pre-association of the building units in solution. These results enhance our understanding of the design principles for supramolecular structures composed of inorganic polyanions and cyclodextrins.
尽管解溶过程在自组装生物结构中很常见，但在晶体结构的设计中却很少得到证实和利用。在本研究中，我们介绍了一种新方法，即使用[Mo8S8O8(OH)8(guest)]2-复合物（由围绕一个客体单元（MoVIO6H4 或草酸盐）的四个[MoV2O2S2]2-片段自缩合形成）作为混沌支架，使天然环糊精的有机-无机杂化体系结晶。我们的研究结果表明，β-环糊精（β-CD）有利于形成宿主-客体复合物，而α-环糊精（α-CD）则会诱导形成具有显著空隙的卡戈米型结构。利用 X 射线衍射（粉末和单晶）、N2 吸附、元素分析和热重分析对这些新化合物进行了全面的表征。此外，利用 1H NMR 滴定和小角 X 射线散射 (SAXS) 进行的溶液研究表明，构建单元在溶液中发生了预结合。这些结果加深了我们对由无机聚阴离子和环糊精组成的超分子结构的设计原理的理解。
{"title":"Cyclic Oxothiomolybdates: Building Blocks for Cyclodextrin-Based Open Frameworks.","authors":"Maxence Lion, Jérôme Marrot, William Shepard, Nathalie Leclerc, Mohamed Haouas, Emmanuel Cadot, Clément Falaise","doi":"10.1002/cplu.202400475","DOIUrl":"10.1002/cplu.202400475","url":null,"abstract":"<p><p>Desolvation processes, though common in self-assembled biological structures, are rarely evidenced and utilized in the design of crystalline architectures. In this study, we introduce a novel approach using the [Mo<sub>8</sub>S<sub>8</sub>O<sub>8</sub>(OH)<sub>8</sub>(guest)]<sup>2-</sup> complex, formed by the self-condensation of four [Mo<sup>V</sup> <sub>2</sub>O<sub>2</sub>S<sub>2</sub>]<sup>2-</sup> fragments around a guest unit (Mo<sup>VI</sup>O<sub>6</sub>H<sub>4</sub> or oxalate), as a chaotropic scaffold for crystallizing hybrid organic-inorganic systems with natural cyclodextrins. Our findings reveal that β-cyclodextrin (β-CD) facilitates the formation of host-guest complexes, while α-cyclodextrin (α-CD) induces the formation of a Kagome-type structure with significant voids. These new compounds were thoroughly characterized using X-ray diffraction (both powder and single-crystal), N<sub>2</sub> adsorption, elemental and thermogravimetric analysis. Additionally, solution studies using <sup>1</sup>H NMR titration and small-angle X-ray scattering (SAXS) demonstrated pre-association of the building units in solution. These results enhance our understanding of the design principles for supramolecular structures composed of inorganic polyanions and cyclodextrins.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400475"},"PeriodicalIF":3.0,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142152696","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rational design of heterogeneous acid catalysts possessing uniform dispersion of active sites plays a significant role in the catalytic performance. In the present work, a coordination polymer, [Zn(4,4´‐bpy)(µ‐Hbtc)(H2O)]∙2H2O (Zn‐CP), was solvothermally synthesized using 4,4´‐bpy (= 4,4´‐bipyridine) and H3btc (= 1,3,5‐benzenetricarboxylic acid) mixed linkers. Single crystal X‐ray analysis of the polymer displayed that Zn‐CP chains were decorated with 4,4´‐bpy having unidentate coordination fashion. Then, the free N atom of the linker in Zn‐CP was functionalized by ‐SO3H groups to afford Zn‐CP‐SO3H with enhanced acidity. The structures were characterized by FT‐IR, thermogravimetric analysis, powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), temperature programmed desorption of NH3 (NH3‐TPD), and field emission scanning electron microscopy (FE‐SEM) analyses. The coordination polymer was employed as heterogeneous catalyst for alcoholysis of epoxides under room conditions. The Zn‐CP‐SO3H exhibited excellent catalytic activity and regioselectivity in the methanolysis of styrene oxide within short reaction time.
合理设计具有均匀分散活性位点的异质酸催化剂对催化性能起着重要作用。本研究利用 4,4´-bpy（= 4,4´-联吡啶）和 H3btc（= 1,3,5-苯三羧酸）混合连接体，通过溶解热合成了配位聚合物 [Zn(4,4´-bpy)(µ-Hbtc)(H2O)]∙2H2O（Zn-CP）。聚合物的单晶 X 射线分析表明，Zn-CP 链被 4,4´-bpy装饰，具有非同一配位方式。然后，Zn-CP 链节的自由 N 原子被 -SO3H 基团官能化，从而得到酸性增强的 Zn-CP-SO3H。通过傅立叶变换红外光谱、热重分析、粉末 X 射线衍射 (XRD)、X 射线光电子能谱 (XPS)、NH3 的温度编程解吸 (NH3-TPD) 以及场发射扫描电子显微镜 (FE-SEM) 分析对这些结构进行了表征。该配位聚合物被用作室温条件下醇解环氧化物的异相催化剂。Zn-CP-SO3H 在短反应时间内对氧化苯乙烯的甲醇分解具有优异的催化活性和区域选择性。
{"title":"Post‐Synthetic Modification of a 1D Mixed‐Linker Zn(II) Coordination Polymer for Acid‐Catalyzed Alcoholysis of Epoxides","authors":"Mahnaz Najafi, Jan Janczak","doi":"10.1002/cplu.202400400","DOIUrl":"https://doi.org/10.1002/cplu.202400400","url":null,"abstract":"Rational design of heterogeneous acid catalysts possessing uniform dispersion of active sites plays a significant role in the catalytic performance. In the present work, a coordination polymer, [Zn(4,4´‐bpy)(µ‐Hbtc)(H2O)]∙2H2O (Zn‐CP), was solvothermally synthesized using 4,4´‐bpy (= 4,4´‐bipyridine) and H3btc (= 1,3,5‐benzenetricarboxylic acid) mixed linkers. Single crystal X‐ray analysis of the polymer displayed that Zn‐CP chains were decorated with 4,4´‐bpy having unidentate coordination fashion. Then, the free N atom of the linker in Zn‐CP was functionalized by ‐SO3H groups to afford Zn‐CP‐SO3H with enhanced acidity. The structures were characterized by FT‐IR, thermogravimetric analysis, powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), temperature programmed desorption of NH3 (NH3‐TPD), and field emission scanning electron microscopy (FE‐SEM) analyses. The coordination polymer was employed as heterogeneous catalyst for alcoholysis of epoxides under room conditions. The Zn‐CP‐SO3H exhibited excellent catalytic activity and regioselectivity in the methanolysis of styrene oxide within short reaction time.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"249 1","pages":""},"PeriodicalIF":3.4,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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