Mandeep Purwa, Gaykwad Chandrakanth, Abhilash Rana, Amirreza Mottafegh, Sanjeev Kumar, Dong-Pyo Kim, Ajay K Singh
Trivalent phosphine catalysis is mostly utilized to activate the carbon-carbon multiple bonds to form carbanion intermediate species and highly sensitive to certain variables. Random manual multi-variables are critical for understanding the batch disabled regeneration of trivalent phosphine chemistry. We need the artificial intelligence-based system which can change the variable based on previously conducted failed experiment. Herein, we report an auto-optimized electro-micro-flow reactor platform for the in-situ reduction of stable P(V) oxide to sensitive P(III) and further utilized for Corey-Fuchs reaction.
{"title":"Auto-Optimized Electro-Flow Reactor Platform for the in-situ Reduction of P(V) Oxide to P(III) and Their Application.","authors":"Mandeep Purwa, Gaykwad Chandrakanth, Abhilash Rana, Amirreza Mottafegh, Sanjeev Kumar, Dong-Pyo Kim, Ajay K Singh","doi":"10.1002/asia.202400438","DOIUrl":"https://doi.org/10.1002/asia.202400438","url":null,"abstract":"<p><p>Trivalent phosphine catalysis is mostly utilized to activate the carbon-carbon multiple bonds to form carbanion intermediate species and highly sensitive to certain variables. Random manual multi-variables are critical for understanding the batch disabled regeneration of trivalent phosphine chemistry. We need the artificial intelligence-based system which can change the variable based on previously conducted failed experiment. Herein, we report an auto-optimized electro-micro-flow reactor platform for the in-situ reduction of stable P(V) oxide to sensitive P(III) and further utilized for Corey-Fuchs reaction.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141454064","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tyson Dais, Sören Schlittenhardt, Mario Ruben, Christopher E Anson, Annie K Powell, Paul G Plieger
Four new Ni16 molecular wheels with the general formula [L4Ni16(RCOO)16(H2O)x(MeOH)12-x] (where H4L = 1,4-bis((E)-((2'-hydroxybenzyl)imino)methyl)-2,3-naphthalenediol, and R = H or Me) have been isolated and structurally characterised. Complexes C1 - C3 (R = Me)were formed using nickel(II) acetate and presented as polymorphs with the same formulation of charged components. The same wheel-like architecture was observed in C4 (R = H), which was prepared using nickel(II) formate, demonstrating the potential for further versatility of the system. In contrast to similar four-fold symmetric Ni(II) wheel clusters, measurements of the static magnetic properties of C1 indicated the presence of dominant antiferromagnetic interactions and an S = 0 ground state.
{"title":"Self-assembly of four Ni16 Molecular Wheels with Capsule and Tubular Supramolecular Architectures.","authors":"Tyson Dais, Sören Schlittenhardt, Mario Ruben, Christopher E Anson, Annie K Powell, Paul G Plieger","doi":"10.1002/asia.202400381","DOIUrl":"https://doi.org/10.1002/asia.202400381","url":null,"abstract":"<p><p>Four new Ni16 molecular wheels with the general formula [L4Ni16(RCOO)16(H2O)x(MeOH)12-x] (where H4L = 1,4-bis((E)-((2'-hydroxybenzyl)imino)methyl)-2,3-naphthalenediol, and R = H or Me) have been isolated and structurally characterised. Complexes C1 - C3 (R = Me)were formed using nickel(II) acetate and presented as polymorphs with the same formulation of charged components. The same wheel-like architecture was observed in C4 (R = H), which was prepared using nickel(II) formate, demonstrating the potential for further versatility of the system. In contrast to similar four-fold symmetric Ni(II) wheel clusters, measurements of the static magnetic properties of C1 indicated the presence of dominant antiferromagnetic interactions and an S = 0 ground state.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141454069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zihang Yin, Yanwei Cao, Wen Sun, Gang Chen, Xianjie Fang, Lin He
3-Methylpyridine holds a pivotal role in organic chemistry as it constitutes a fundamental structure in numerous biologically active compounds. Its significance is underscored by its involvement in synthesizing vitamin B3 and developing pyridine insecticides, garnering considerable attention. Consequently, chemists have dedicated efforts to devising efficient and environmentally friendly methods for its preparation. This review systematically reviews several synthetic routes to 3-methylpyridine, alongside recent advancements, while summarizing its application progress in various organic transformations.
{"title":"3-Methylpyridine: Synthesis and Applications.","authors":"Zihang Yin, Yanwei Cao, Wen Sun, Gang Chen, Xianjie Fang, Lin He","doi":"10.1002/asia.202400467","DOIUrl":"https://doi.org/10.1002/asia.202400467","url":null,"abstract":"<p><p>3-Methylpyridine holds a pivotal role in organic chemistry as it constitutes a fundamental structure in numerous biologically active compounds. Its significance is underscored by its involvement in synthesizing vitamin B3 and developing pyridine insecticides, garnering considerable attention. Consequently, chemists have dedicated efforts to devising efficient and environmentally friendly methods for its preparation. This review systematically reviews several synthetic routes to 3-methylpyridine, alongside recent advancements, while summarizing its application progress in various organic transformations.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141454062","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Macrocycles are essential in protein-protein interactions and the preferential intake of bioactive scaffolds. Macrocycles are commonly synthesized by late-stage macrolactonizations, macrolactamizations, transition metal-catalyzed ring-closing metathesis, S-S bond-forming reactions, and copper-catalyzed alkyne-azide cycloaddition. Recently, transition metal-catalyzed C-H activation strategies have gained significant interest among chemists to synthesize macrocycles. This article provides a comprehensive overview of the transition metal-catalyzed macrocyclization via C-H bond functionalization of heterocycle-containing peptides, annulations, and heterocycle-ring construction through direct C-H bond functionalization. In the first part, palladium salt catalyzed coupling with indolyl C(sp3)-H and C(sp2)-H bonds for macrocyclization is reported. The second part summarizes rhodium-catalyzed macrocyclizations via site-selective C-H bond functionalization. Earth-abundant, less toxic 3d metal salt Mn-catalyzed cyclizations are reported in the latter part. This summary is expected to spark interest in emerging methods of macrocycle production among organic synthesis and chemical biology practitioners, helping to develop the discipline. We hope that this mini-review will also inspire synthetic chemists to explore new and broadly applicable C-C bond-forming strategies for macrocyclization via intramolecular C-H activation.
{"title":"Recent Progress on Transition Metal Catalyzed Macrocyclizations Based on C-H Bond Activation at Heterocyclic Scaffolds.","authors":"Sarbojit Das, Tapan Kumar Pradhan, Rajarshi Samanta","doi":"10.1002/asia.202400397","DOIUrl":"https://doi.org/10.1002/asia.202400397","url":null,"abstract":"<p><p>Macrocycles are essential in protein-protein interactions and the preferential intake of bioactive scaffolds. Macrocycles are commonly synthesized by late-stage macrolactonizations, macrolactamizations, transition metal-catalyzed ring-closing metathesis, S-S bond-forming reactions, and copper-catalyzed alkyne-azide cycloaddition. Recently, transition metal-catalyzed C-H activation strategies have gained significant interest among chemists to synthesize macrocycles. This article provides a comprehensive overview of the transition metal-catalyzed macrocyclization via C-H bond functionalization of heterocycle-containing peptides, annulations, and heterocycle-ring construction through direct C-H bond functionalization. In the first part, palladium salt catalyzed coupling with indolyl C(sp3)-H and C(sp2)-H bonds for macrocyclization is reported. The second part summarizes rhodium-catalyzed macrocyclizations via site-selective C-H bond functionalization. Earth-abundant, less toxic 3d metal salt Mn-catalyzed cyclizations are reported in the latter part. This summary is expected to spark interest in emerging methods of macrocycle production among organic synthesis and chemical biology practitioners, helping to develop the discipline. We hope that this mini-review will also inspire synthetic chemists to explore new and broadly applicable C-C bond-forming strategies for macrocyclization via intramolecular C-H activation.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141454068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nazir Ud Din Mir, Veerappan Karthik, Kalimuthu Abirami Sundari, Amarajyothi Dhakshinamoorthy, Shyam Biswas
Development, rapid detection and quantification of anticancer drugs in biological samples are crucial for effective drug monitoring. The present work describes the design of a metal-organic framework (MOF) between Hf(IV) ion and 2-(thiophene-2-carboxamido)terephthalic acid linker (surface area = 571 m² g-1). Desolvated 1' displayed highly discriminative fluorescence sensing property for the anti-neoplastic drug flutamide and biomolecule hemin in aqueous medium in the presence of co-exiting biomolecules and ions. The MOF's response time for sensing flutamide and hemin was less than 5 s with low detection limits 1.5 and 0.08 nM respectively. Additionally, the MOF also demonstrated recyclability up to five cycles and maintained its sensing ability across different pH media, various water samples, and biological fluids. Experimental and theoretical analyses suggested photoinduced electron transfer and inner-filter effect in the presence of flutamide and Förster resonance energy transfer in the presence of hemin are most likely reasons behind the fluorescence quenching of MOF. Furthermore, the MOF demonstrated catalytic activity in Friedel-Crafts alkylation reactions, providing a 96% yield with slight decay in its activity over four uses. The enhanced activity of 1' is due to the functionalized thiophene moities through hydrogen bond donating sites, confirmed by series of control experiments.
{"title":"A thiophene functionalized Hf(IV) organic framework for the detection of anti-neoplastic drug flutamide and biomolecule hemin and catalysis of Friedel-Crafts alkylation.","authors":"Nazir Ud Din Mir, Veerappan Karthik, Kalimuthu Abirami Sundari, Amarajyothi Dhakshinamoorthy, Shyam Biswas","doi":"10.1002/asia.202400274","DOIUrl":"https://doi.org/10.1002/asia.202400274","url":null,"abstract":"<p><p>Development, rapid detection and quantification of anticancer drugs in biological samples are crucial for effective drug monitoring. The present work describes the design of a metal-organic framework (MOF) between Hf(IV) ion and 2-(thiophene-2-carboxamido)terephthalic acid linker (surface area = 571 m² g-1). Desolvated 1' displayed highly discriminative fluorescence sensing property for the anti-neoplastic drug flutamide and biomolecule hemin in aqueous medium in the presence of co-exiting biomolecules and ions. The MOF's response time for sensing flutamide and hemin was less than 5 s with low detection limits 1.5 and 0.08 nM respectively. Additionally, the MOF also demonstrated recyclability up to five cycles and maintained its sensing ability across different pH media, various water samples, and biological fluids. Experimental and theoretical analyses suggested photoinduced electron transfer and inner-filter effect in the presence of flutamide and Förster resonance energy transfer in the presence of hemin are most likely reasons behind the fluorescence quenching of MOF. Furthermore, the MOF demonstrated catalytic activity in Friedel-Crafts alkylation reactions, providing a 96% yield with slight decay in its activity over four uses. The enhanced activity of 1' is due to the functionalized thiophene moities through hydrogen bond donating sites, confirmed by series of control experiments.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141454063","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel hybrid network was synthesized in two steps: the first step involved the attachment of glycidyl methacrylate (GMA) to octa(aminophenyl) silsesquioxane (OAPS) through a ring‐opening reaction, forming a hybrid dendrimer structure, and the second step involved the cross‐linking of hybrid dendrimer using an azobisisobutyronitrile initiator to create the final hybrid network of OAPS‐GMA. The synthesized hybrid material was comprehensively characterized using fourier transform infrared Spectroscopy (FTIR), nuclear magnetic resonance ((1H, 13C, and 29Si NMR) spectroscopy, thermogravimetric Analysis (TGA), and scanning electron microscopy (SEM). The BET surface area was found to be 25.44 m²/g, and significant 2.341 cm³/g of total pore volume was observed. The TGA analysis shows that the material is highly stable up to 450 oC. The synthesized network demonstrated remarkable adsorption capacities for iodine and dyes. It exhibited an iodine adsorption capacity of 3.4g/g from vapors and 874mg/g from solution. Additionally, it showed significant adsorption capacities for Rhodamine B and Congo red, with values of 762mg/g and 517mg/g, respectively. This study not only provides a novel method for preparing GMA‐functionalized silsesquioxane‐based porous hybrid polymers but also contributes to advancing solutions for environmental pollution issues.
{"title":"Hybrid Dendrimer Network based on Silsesquioxane and glycidyl methacrylate for Enhanced Adsorption of Iodine and Dyes in Environmental Remediation.","authors":"saddam Hussain, Hongzhi Liu, Kunthom Rungthip","doi":"10.1002/asia.202400584","DOIUrl":"https://doi.org/10.1002/asia.202400584","url":null,"abstract":"A novel hybrid network was synthesized in two steps: the first step involved the attachment of glycidyl methacrylate (GMA) to octa(aminophenyl) silsesquioxane (OAPS) through a ring‐opening reaction, forming a hybrid dendrimer structure, and the second step involved the cross‐linking of hybrid dendrimer using an azobisisobutyronitrile initiator to create the final hybrid network of OAPS‐GMA. The synthesized hybrid material was comprehensively characterized using fourier transform infrared Spectroscopy (FTIR), nuclear magnetic resonance ((1H, 13C, and 29Si NMR) spectroscopy, thermogravimetric Analysis (TGA), and scanning electron microscopy (SEM). The BET surface area was found to be 25.44 m²/g, and significant 2.341 cm³/g of total pore volume was observed. The TGA analysis shows that the material is highly stable up to 450 oC. The synthesized network demonstrated remarkable adsorption capacities for iodine and dyes. It exhibited an iodine adsorption capacity of 3.4g/g from vapors and 874mg/g from solution. Additionally, it showed significant adsorption capacities for Rhodamine B and Congo red, with values of 762mg/g and 517mg/g, respectively. This study not only provides a novel method for preparing GMA‐functionalized silsesquioxane‐based porous hybrid polymers but also contributes to advancing solutions for environmental pollution issues.","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":4.568,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141511019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two hydroxy rich hypercrosslinked POPs, namely Ph/Tt-POP have been developed by facile one-pot condensation polymerization strategy. The high surface areas of both the Ph/Tt-POP (1057 and 893 m2g-1, respectively), and the heteroatom functionality in the POP framework instigated us to explore our material for CO2 adsorption study. The CO2 uptake capacities in Ph/Tt-POP are found to be 2.45 and 2.2 mmol g-1, at 273 K respectively. in-situ static 13C NMR experiment shows that CO2 molecules in Tt-POP appear to be less mobile than those in Ph-POP which probably due to the presence of triazine functional groups along with high abundant -OH groups in the Tt-POP framework. An in-depth study of the CO2 adsorption mechanism by density functional theory (DFT) calculations also shows that CO2 adsorption at the cages formed by two benzyl rings represents the most stable interaction and CO2 molecule is more favorably adsorbed on the Ph-POP with the more negative interaction energies values compared to that of Tt-POP. Non-covalent interaction (NCI) plot revealed that CO2 molecule is adsorbed more on the Ph-POP than Tt-POP, which can be explained by hydrogen bond formation in case of Tt-POP repeating units turning aside CO2 molecule to interact with the Ph component.
{"title":"Harmonizing Between Chemical Functionality and Surface Area of Porous Organic Polymeric Nanotraps for Tuning Carbon Dioxide Capture.","authors":"Dhruba Jyoti Deka, Chandan Biswas, Ratul Paul, Jiabin Xu, Yining Huang, Duy Quang Dao, John Mondal","doi":"10.1002/asia.202400515","DOIUrl":"https://doi.org/10.1002/asia.202400515","url":null,"abstract":"<p><p>Two hydroxy rich hypercrosslinked POPs, namely Ph/Tt-POP have been developed by facile one-pot condensation polymerization strategy. The high surface areas of both the Ph/Tt-POP (1057 and 893 m2g-1, respectively), and the heteroatom functionality in the POP framework instigated us to explore our material for CO2 adsorption study. The CO2 uptake capacities in Ph/Tt-POP are found to be 2.45 and 2.2 mmol g-1, at 273 K respectively. in-situ static 13C NMR experiment shows that CO2 molecules in Tt-POP appear to be less mobile than those in Ph-POP which probably due to the presence of triazine functional groups along with high abundant -OH groups in the Tt-POP framework. An in-depth study of the CO2 adsorption mechanism by density functional theory (DFT) calculations also shows that CO2 adsorption at the cages formed by two benzyl rings represents the most stable interaction and CO2 molecule is more favorably adsorbed on the Ph-POP with the more negative interaction energies values compared to that of Tt-POP. Non-covalent interaction (NCI) plot revealed that CO2 molecule is adsorbed more on the Ph-POP than Tt-POP, which can be explained by hydrogen bond formation in case of Tt-POP repeating units turning aside CO2 molecule to interact with the Ph component.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":4.1,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141425846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jaeseong Heo, Hyeowon Kim, Jiyeong Park, Nurwarrohman Andre Sasongko, Mincheol Jeong, Jaeeun Han, Taeji Seo, Yujeong Ji, Jiyoung Han, Myeongkee Park
This study compared the photoluminescence (PL) stabilities of formamidinium (FA) and methylammonium (MA) in lead iodide perovskite quantum dots (QDs). To exclude other factors, such as size and purity, that may affect stability, MAPbI3 and FAPbI3 QDs with nearly identical sizes (~10.0 nm) were synthesized by controlling the ligand concentration and synthesis temperature. Transmission electron microscopy images and X-ray diffraction patterns confirmed homogeneous single-phase perovskite structures. Additionally, the bandgaps and sizes of the synthesized QDs closely matched those of the infinite quantum well model, which guaranteed that the photostability was solely caused by the different organic molecules in the two QDs. We analyzed the PL peak centers and full-width at half maximum of the QDs for 32 days. The enhanced stability of FAPbI3 was found to be caused by the nearly zero redshift (1.615 eV) of its PL peak, in contrast to the redshift (1.685→1.670 eV) of that of MAPbI3.
{"title":"Long-term Comparisons of Photoluminescence Affected by Organic Cations of Formamidinium and Methylammonium in Monophasic Lead Iodide Perovskite Quantum Dots.","authors":"Jaeseong Heo, Hyeowon Kim, Jiyeong Park, Nurwarrohman Andre Sasongko, Mincheol Jeong, Jaeeun Han, Taeji Seo, Yujeong Ji, Jiyoung Han, Myeongkee Park","doi":"10.1002/asia.202400347","DOIUrl":"https://doi.org/10.1002/asia.202400347","url":null,"abstract":"<p><p>This study compared the photoluminescence (PL) stabilities of formamidinium (FA) and methylammonium (MA) in lead iodide perovskite quantum dots (QDs). To exclude other factors, such as size and purity, that may affect stability, MAPbI3 and FAPbI3 QDs with nearly identical sizes (~10.0 nm) were synthesized by controlling the ligand concentration and synthesis temperature. Transmission electron microscopy images and X-ray diffraction patterns confirmed homogeneous single-phase perovskite structures. Additionally, the bandgaps and sizes of the synthesized QDs closely matched those of the infinite quantum well model, which guaranteed that the photostability was solely caused by the different organic molecules in the two QDs. We analyzed the PL peak centers and full-width at half maximum of the QDs for 32 days. The enhanced stability of FAPbI3 was found to be caused by the nearly zero redshift (1.615 eV) of its PL peak, in contrast to the redshift (1.685→1.670 eV) of that of MAPbI3.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":4.1,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141425847","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Richard Winpenny, Tom S Bennett, Selena J Lockyer, Deepak Asthana, George F S Whitehead, Inigo J Vitorica-Yrezabal, Grigore A Timco, Eric J L McInnes
Mono- and bis-salen functionalised [2]rotaxanes have been synthesised from the esterification of [2]rotaxanes containing phenol-terminated threads (salen = N,N'-bis(salicylidene)ethylenediamine). The [2]rotaxanes have general formula [RH][Cr7NiF8(O2CtBu)16], where [RH]+ is a thread with a central secondary ammonium site that templates a [Cr7NiF8(O2CtBu)16]- ring. The threads are terminated at one or both ends by carboxylic acid functionalised salen groups. The {M(salen)} groups can be free-base [M = (H+)2] or metallated [M = Cu2+, Ni2+, (VO)2+]. The [2]rotaxanes have been characterised by single crystal XRD and solid- and solution-state EPR spectroscopy. Where two paramagnetic M ions are involved [M = Cu2+ and/or (VO)2+] the [2]rotaxanes contain three electron spin S = ½ centres, since the {Cr7Ni} ring has an S = ½ ground state which is well isolated at low temperatures. These three-spin [2]rotaxanes have been characterised in solution by pulsed dipolar EPR spectroscopies (DEER, also known as PELDOR, and RIDME). The M···M and M···{Cr7Ni} interactions measured are consistent with dipolar interactions and also with the distances from single crystal XRD.
通过酯化含有苯酚末端螺纹(salen = N,N'-双(水杨醛基)乙二胺)的[2]轮烷,合成了单-和双-水杨醛官能化的[2]轮烷。[2]轮烷的通式为[RH][Cr7NiF8(O2CtBu)16],其中[RH]+是带有中心仲铵位点的螺纹,该位点模板为[Cr7NiF8(O2CtBu)16]环。螺纹的一端或两端由羧酸官能化的沙仑基团终止。{M(salen)}基团可以是自由碱[M = (H+)2]或金属化[M = Cu2+、Ni2+、(VO)2+]。我们通过单晶 XRD 以及固态和溶态 EPR 光谱对 [2]rotaxanes 进行了表征。当涉及两个顺磁 M 离子 [M = Cu2+ 和/或 (VO)2+] 时,[2]轮烷含有三个电子自旋 S = ½ 中心,因为{Cr7Ni}环具有 S = ½ 基态,在低温下可以很好地隔离。这些三自旋 [2]rotaxanes 在溶液中通过脉冲双极 EPR 光谱(DEER,又称 PELDOR 和 RIDME)进行了表征。测得的 M-M 和 M---{Cr7Ni}相互作用与偶极相互作用以及单晶 XRD 的距离一致。
{"title":"Two- and Three-Spin Hybrid Inorganic-Organic [2]Rotaxanes Containing Metallated Salen Groups.","authors":"Richard Winpenny, Tom S Bennett, Selena J Lockyer, Deepak Asthana, George F S Whitehead, Inigo J Vitorica-Yrezabal, Grigore A Timco, Eric J L McInnes","doi":"10.1002/asia.202400641","DOIUrl":"https://doi.org/10.1002/asia.202400641","url":null,"abstract":"<p><p>Mono- and bis-salen functionalised [2]rotaxanes have been synthesised from the esterification of [2]rotaxanes containing phenol-terminated threads (salen = N,N'-bis(salicylidene)ethylenediamine). The [2]rotaxanes have general formula [RH][Cr7NiF8(O2CtBu)16], where [RH]+ is a thread with a central secondary ammonium site that templates a [Cr7NiF8(O2CtBu)16]- ring. The threads are terminated at one or both ends by carboxylic acid functionalised salen groups. The {M(salen)} groups can be free-base [M = (H+)2] or metallated [M = Cu2+, Ni2+, (VO)2+]. The [2]rotaxanes have been characterised by single crystal XRD and solid- and solution-state EPR spectroscopy. Where two paramagnetic M ions are involved [M = Cu2+ and/or (VO)2+] the [2]rotaxanes contain three electron spin S = ½ centres, since the {Cr7Ni} ring has an S = ½ ground state which is well isolated at low temperatures. These three-spin [2]rotaxanes have been characterised in solution by pulsed dipolar EPR spectroscopies (DEER, also known as PELDOR, and RIDME). The M···M and M···{Cr7Ni} interactions measured are consistent with dipolar interactions and also with the distances from single crystal XRD.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":4.1,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141425848","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Formic acid (HCOOH) is a highly energy-efficient product of electrochemical CO2 reduction reaction (CO2RR). Bismuth-based catalysts have shown promise in the conversion of CO2 to formic acid, but there is still a great need for further improvement in selectivity and activity. Herein, we report the preparation of Bi nanosheets decorated by cerium oxide nanoparticles (CeOx) with high Ce3+/Ce4+ ratio and rich oxygen vacancies. The CeOx nanoparticles affect on the electronic structures of bismuth, enhance the CO2 adsorption, and thus promote the CO2RR properties of Bi nanosheets. Compared with elemental Bi nanosheets, the hetero-structured CeOx/Bi nanosheets exhibit much higher activity over a wide potential window, showing a current density of 16.1 mA cm-2 with a Faradaic efficiency of 91.1% at -0.9 V vs. reversible hydrogen electrode.
甲酸(HCOOH)是电化学二氧化碳还原反应(CO2RR)的高能效产物。铋基催化剂在将 CO2 转化为甲酸的过程中显示出良好的前景,但仍亟需进一步提高其选择性和活性。在此,我们报告了由具有高 Ce3+/Ce4+ 比值和丰富氧空位的氧化铈纳米颗粒(CeOx)装饰的 Bi 纳米片的制备方法。CeOx 纳米粒子影响了铋的电子结构,增强了对 CO2 的吸附,从而促进了 Bi 纳米片的 CO2RR 特性。与元素铋纳米片相比,异质结构的 CeOx/Bi 纳米片在较宽的电位窗口内表现出更高的活性,与可逆氢电极相比,在 -0.9 V 电压下,电流密度为 16.1 mA cm-2,法拉第效率为 91.1%。
{"title":"Promotion of CO2 Electroreduction on Bismuth Nanosheets with Cerium Oxide nanoparticles.","authors":"Yue Guan, Siqian Wu, Huizi Huang, Zhejiaji Zhu, Wenjing Tian, Anxiang Yin","doi":"10.1002/asia.202400296","DOIUrl":"https://doi.org/10.1002/asia.202400296","url":null,"abstract":"<p><p>Formic acid (HCOOH) is a highly energy-efficient product of electrochemical CO2 reduction reaction (CO2RR). Bismuth-based catalysts have shown promise in the conversion of CO2 to formic acid, but there is still a great need for further improvement in selectivity and activity. Herein, we report the preparation of Bi nanosheets decorated by cerium oxide nanoparticles (CeOx) with high Ce3+/Ce4+ ratio and rich oxygen vacancies. The CeOx nanoparticles affect on the electronic structures of bismuth, enhance the CO2 adsorption, and thus promote the CO2RR properties of Bi nanosheets. Compared with elemental Bi nanosheets, the hetero-structured CeOx/Bi nanosheets exhibit much higher activity over a wide potential window, showing a current density of 16.1 mA cm-2 with a Faradaic efficiency of 91.1% at -0.9 V vs. reversible hydrogen electrode.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":4.1,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141416956","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}