Ziteng Guo, Hao Yu, Junjuan Shi, Ningxu Han, Guanglu Wu, Houyu Zhang, Bingling Li, Ming Wang
For artificial supramolecular architectures designed to mimic biological systems, achieving different pathway synthesis is challenging due to the requirement of multiple stable and interconvertible intermediates. Here, we propose a novel “inner‐outer steric synergy” strategy and investigate controllable pathway engineering for the synthesis of specific structures. Firstly, three structures (Ring‐Pd2LA2, Bowl‐Pd2LA3 or Cage‐Pd2LA4) with interconversion properties were selectively formed by assembling externally modified ligand LA with Pd(II). Furthermore, Ring‐Pd2LA2 can further assemble with the ligand LB with inner steric hindrance to generate heteroleptic trans‐Pd2LA2LB2 cage, while Bowl‐Pd2LA3, as an intermediate, can assemble with LB to form Pd2LA3LB. It is noteworthy that Ring‐Pd2LA2, Bowl‐Pd2LA3, and Cage‐Pd2LA4 can interconvert under specific conditions, enabling the synthesis of Pd2LA3LB and trans‐Pd2LA2LB2 through 10 and 16 pathways, respectively. This research not only introduces a novel strategy for constructing heteroleptic cages but also demonstrates the achievement of pathway engineering.
{"title":"Pathway Engineering in Pd‐Based Supramolecular Cage Synthesis via Inner‐Outer Steric Synergy","authors":"Ziteng Guo, Hao Yu, Junjuan Shi, Ningxu Han, Guanglu Wu, Houyu Zhang, Bingling Li, Ming Wang","doi":"10.1002/anie.202425369","DOIUrl":"https://doi.org/10.1002/anie.202425369","url":null,"abstract":"For artificial supramolecular architectures designed to mimic biological systems, achieving different pathway synthesis is challenging due to the requirement of multiple stable and interconvertible intermediates. Here, we propose a novel “inner‐outer steric synergy” strategy and investigate controllable pathway engineering for the synthesis of specific structures. Firstly, three structures (Ring‐Pd2LA2, Bowl‐Pd2LA3 or Cage‐Pd2LA4) with interconversion properties were selectively formed by assembling externally modified ligand LA with Pd(II). Furthermore, Ring‐Pd2LA2 can further assemble with the ligand LB with inner steric hindrance to generate heteroleptic trans‐Pd2LA2LB2 cage, while Bowl‐Pd2LA3, as an intermediate, can assemble with LB to form Pd2LA3LB. It is noteworthy that Ring‐Pd2LA2, Bowl‐Pd2LA3, and Cage‐Pd2LA4 can interconvert under specific conditions, enabling the synthesis of Pd2LA3LB and trans‐Pd2LA2LB2 through 10 and 16 pathways, respectively. This research not only introduces a novel strategy for constructing heteroleptic cages but also demonstrates the achievement of pathway engineering.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"178 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435468","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}
The chemoselective reaction are vital for fine chemicals, which requires economical and environmentally friendly catalysts. In order to improve the selectivity of multi‐reaction competition, herein, we propose a novel ionic‐fence strategy to synthesize heterogeneous catalyst for efficient hydrogenation. Practically, UIO‐66 metal‐organic frameworks (MOF) modified with pyridinium‐linker has been constructed through post‐synthetic chains with paired anion via quaternization and ion exchange to form ionic‐fence MOF (IFMOF‐Cl), which can manage the adsorption mode of nitro substrate, further confine the formation of metal nanoparticles with high dispersity. The optimal Au@IFMOF‐Cl catalyst demonstrates satisfactory selectivity for hydrogenation of nitro group compared to acetylene group in 4‐nitrophenylacetylene, specifically, it owns a high yield of 4‐aminophenylacetylene (~97%) with ultra‐high catalytic efficiency (3880 h‐1 TOF) and long stability, far superior to other catalysts without ionic fence effect. Adsorption experiments and density functional theory studies reveal that the incorporation of ionic fence could modulate the adsorption energy of nitro group, which is responsible for the high selectivity enhancement. Notably, this ionic‐fence strategy exhibits comprehensive universality towards a wide range of substrates (23 kinds in total), providing a promising avenue for precisely engineering the internal microenvironments of catalysts to achieve highly selective synthesis of fine chemicals.
{"title":"Ionic‐fence Effect in Au Nanoparticle‐loaded UiO‐66 Metal–Organic Frameworks for Highly Chemoselective Hydrogenation","authors":"Yicheng Zhong, Peisen Liao, Pingping Jiang, Yuhao Zhang, Jiawei Kang, Sizhuo Xie, Rongyu Feng, Yanan Fan, Qinghua Liu, Guangqin Li","doi":"10.1002/anie.202501821","DOIUrl":"https://doi.org/10.1002/anie.202501821","url":null,"abstract":"The chemoselective reaction are vital for fine chemicals, which requires economical and environmentally friendly catalysts. In order to improve the selectivity of multi‐reaction competition, herein, we propose a novel ionic‐fence strategy to synthesize heterogeneous catalyst for efficient hydrogenation. Practically, UIO‐66 metal‐organic frameworks (MOF) modified with pyridinium‐linker has been constructed through post‐synthetic chains with paired anion via quaternization and ion exchange to form ionic‐fence MOF (IFMOF‐Cl), which can manage the adsorption mode of nitro substrate, further confine the formation of metal nanoparticles with high dispersity. The optimal Au@IFMOF‐Cl catalyst demonstrates satisfactory selectivity for hydrogenation of nitro group compared to acetylene group in 4‐nitrophenylacetylene, specifically, it owns a high yield of 4‐aminophenylacetylene (~97%) with ultra‐high catalytic efficiency (3880 h‐1 TOF) and long stability, far superior to other catalysts without ionic fence effect. Adsorption experiments and density functional theory studies reveal that the incorporation of ionic fence could modulate the adsorption energy of nitro group, which is responsible for the high selectivity enhancement. Notably, this ionic‐fence strategy exhibits comprehensive universality towards a wide range of substrates (23 kinds in total), providing a promising avenue for precisely engineering the internal microenvironments of catalysts to achieve highly selective synthesis of fine chemicals.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435466","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}
Hengyue Chen, Pengchao Ruan, Hao Zhang, Zeinhom M. El-Bahy, Mohamed M. Ibrahim, Bingan Lu, Jiang Zhou
Despite the widespread interest in electrolytic Zn-MnO2 batteries with excellent output voltage and high theoretical capacity, the spontaneous disproportionation reaction of free Mn3+ along with the disorderly deposited inactive MnO2 results in the low Mn2+/MnO2 conversion reversibility, which seriously affects their cycling stability. Here, we propose a novel aqueous SiO2 colloidal electrolyte with FeSO4 mediator (denoted as SF electrolyte) based on a bidirectional electrochemical-chemical model to achieve dual regulation of the MnO2 deposition/dissolution process. During the charging process, the SiO2 colloidal particles located at the carbon felt interface and the electrolyte bulk phase simultaneously provide sufficient disproportionation sites for the diffused Mn3+ to guide the orderly rapid deposition of MnO2. Meanwhile, the introduction of Fe2+ mediators during the discharge process can sufficiently react with MnO2 on the SiO2 particles in the electrolyte, thereby further enabling the efficient conversion of Mn2+/MnO2. Consequently, electrolytic Zn-MnO2 battery with SF electrolyte can stably run for 550 cycles at 10 mA h cm-2 and achieve superior reversibility at a high area capacity of 20 mA h cm-2. This work demonstrates the feasibility of colloidal electrolytes in modulating electrochemical-chemical processes to stabilize electrolytic Zn-MnO2 batteries.
{"title":"Achieving Highly Reversible Mn2+/MnO2 Conversion Reaction in Electrolytic Zn-MnO2 Batteries via Electrochemical-Chemical Process Regulation","authors":"Hengyue Chen, Pengchao Ruan, Hao Zhang, Zeinhom M. El-Bahy, Mohamed M. Ibrahim, Bingan Lu, Jiang Zhou","doi":"10.1002/anie.202423999","DOIUrl":"https://doi.org/10.1002/anie.202423999","url":null,"abstract":"Despite the widespread interest in electrolytic Zn-MnO2 batteries with excellent output voltage and high theoretical capacity, the spontaneous disproportionation reaction of free Mn3+ along with the disorderly deposited inactive MnO2 results in the low Mn2+/MnO2 conversion reversibility, which seriously affects their cycling stability. Here, we propose a novel aqueous SiO2 colloidal electrolyte with FeSO4 mediator (denoted as SF electrolyte) based on a bidirectional electrochemical-chemical model to achieve dual regulation of the MnO2 deposition/dissolution process. During the charging process, the SiO2 colloidal particles located at the carbon felt interface and the electrolyte bulk phase simultaneously provide sufficient disproportionation sites for the diffused Mn3+ to guide the orderly rapid deposition of MnO2. Meanwhile, the introduction of Fe2+ mediators during the discharge process can sufficiently react with MnO2 on the SiO2 particles in the electrolyte, thereby further enabling the efficient conversion of Mn2+/MnO2. Consequently, electrolytic Zn-MnO2 battery with SF electrolyte can stably run for 550 cycles at 10 mA h cm-2 and achieve superior reversibility at a high area capacity of 20 mA h cm-2. This work demonstrates the feasibility of colloidal electrolytes in modulating electrochemical-chemical processes to stabilize electrolytic Zn-MnO2 batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"28 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435642","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}
Jong Hyeok Park, Min Su Choi, Sang Goo Kang, Jaehoon Choi, Jeonghyun Ko
Coupling gel polymer electrolytes (GPEs) with high‐Ni cathodes (NCM) has emerged as a compelling approach for high‐energy lithium‐ion batteries, capable of circumventing NCM failure modes in liquid electrolytes. However, a detailed origin of capacity decay caused by residual monomers from an uncontrollable curing process has been largely ignored. Here, we report an in‐depth investigation into the side reactions of unreacted monomers within typical GPEs at the NCM cathode interfaces by utilizing multiscale spectroscopy combined with theoretical calculations. We evaluate conversion rate‐interphase structure correlation, revealing that interfacial evolution is highly dependent on residual monomer content. Specifically, the degradation chemistry in NCM cathodes with thermally cured gel polymer electrolytes (TC‐GPEs) is governed by monomer‐initiated interphase reconstruction, leading to an imbalanced interphase growth mode with organic‐rich species and retarded diffusion kinetics through the electrode. We further reveal that organic ether/ester‐based byproducts, caused by the oxidative decomposition of unreacted monomers during the initial charging step, are the key factor for the acceleration of NCM failure modes. This study elucidates the multiscale fading mechanism in the NCM||GPE system, providing improved insights into interphase issues in typical GPEs and facilitating the further development of long‐life NCM||GPE prototypes for commercial applications.
{"title":"Residual Monomer‐Induced Side Reactions in Gel Polymer Electrolytes: Unveiled High‐Ni Cathode Failure in Lithium Batteries","authors":"Jong Hyeok Park, Min Su Choi, Sang Goo Kang, Jaehoon Choi, Jeonghyun Ko","doi":"10.1002/anie.202424568","DOIUrl":"https://doi.org/10.1002/anie.202424568","url":null,"abstract":"Coupling gel polymer electrolytes (GPEs) with high‐Ni cathodes (NCM) has emerged as a compelling approach for high‐energy lithium‐ion batteries, capable of circumventing NCM failure modes in liquid electrolytes. However, a detailed origin of capacity decay caused by residual monomers from an uncontrollable curing process has been largely ignored. Here, we report an in‐depth investigation into the side reactions of unreacted monomers within typical GPEs at the NCM cathode interfaces by utilizing multiscale spectroscopy combined with theoretical calculations. We evaluate conversion rate‐interphase structure correlation, revealing that interfacial evolution is highly dependent on residual monomer content. Specifically, the degradation chemistry in NCM cathodes with thermally cured gel polymer electrolytes (TC‐GPEs) is governed by monomer‐initiated interphase reconstruction, leading to an imbalanced interphase growth mode with organic‐rich species and retarded diffusion kinetics through the electrode. We further reveal that organic ether/ester‐based byproducts, caused by the oxidative decomposition of unreacted monomers during the initial charging step, are the key factor for the acceleration of NCM failure modes. This study elucidates the multiscale fading mechanism in the NCM||GPE system, providing improved insights into interphase issues in typical GPEs and facilitating the further development of long‐life NCM||GPE prototypes for commercial applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"49 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435437","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}
Josh Leverett, Ghazal Baghestani, Thanh Tran-Phu, Jodie A. Yuwono, Priyank Kumar, Bernt Johannessen, Darcy Simondson, Haotien Wen, Shery L. Y. Chang, Antonio Tricoli, Alexandr N. Simonov, Liming Dai, Rose Amal, Rahman Daiyan, Rosalie K. Hocking
SACs are an important class of materials that mediate chemical reduction reactions, a key subset of which is Ni within a carbon support for the electrochemical CO2 reduction reaction (CO2RR). However, how the metal atom/clusters and carbon‐based support act in concert to catalyze CO2RR is not well understood, with most reports attributing activity solely to the Ni‐Nx/C moieties. To address this gap, we have undertaken a mechanistic investigation, employing in situ X‐ray absorption spectroscopy (XAS) coupled with electrochemical studies and DFT calculations to further understand how Ni single atoms work in conjunction with the nitrogen‐doped carbon matrix to promote CO2RR to CO, and how the presence of impurities such as those present in CO2‐containing waste flue gases (including NOx, and CN‐) changes the catalyst upon reduction. In contrast to previous works, we do not find strong evidence for a purely metal‐based reduction upon application of negative reductive potentials. Instead, we present evidence for an increase in the equatorial vs. axial splitting of Ni, consistent with electrons moving onto the reactants via the Ni single atom 3dz2 orbital. In addition, we demonstrate a transient poisoning mechanism of the Ni SAC by nitrite and thiocyanate, explaining the recovery of activity during CO2RR.
{"title":"Direct Observation of Electron Donation onto the Reactants and a Transient Poisoning Mechanism During CO2 Electroreduction on Ni Single Atom Catalysts","authors":"Josh Leverett, Ghazal Baghestani, Thanh Tran-Phu, Jodie A. Yuwono, Priyank Kumar, Bernt Johannessen, Darcy Simondson, Haotien Wen, Shery L. Y. Chang, Antonio Tricoli, Alexandr N. Simonov, Liming Dai, Rose Amal, Rahman Daiyan, Rosalie K. Hocking","doi":"10.1002/anie.202424087","DOIUrl":"https://doi.org/10.1002/anie.202424087","url":null,"abstract":"SACs are an important class of materials that mediate chemical reduction reactions, a key subset of which is Ni within a carbon support for the electrochemical CO2 reduction reaction (CO2RR). However, how the metal atom/clusters and carbon‐based support act in concert to catalyze CO2RR is not well understood, with most reports attributing activity solely to the Ni‐Nx/C moieties. To address this gap, we have undertaken a mechanistic investigation, employing in situ X‐ray absorption spectroscopy (XAS) coupled with electrochemical studies and DFT calculations to further understand how Ni single atoms work in conjunction with the nitrogen‐doped carbon matrix to promote CO2RR to CO, and how the presence of impurities such as those present in CO2‐containing waste flue gases (including NOx, and CN‐) changes the catalyst upon reduction. In contrast to previous works, we do not find strong evidence for a purely metal‐based reduction upon application of negative reductive potentials. Instead, we present evidence for an increase in the equatorial vs. axial splitting of Ni, consistent with electrons moving onto the reactants via the Ni single atom 3dz2 orbital. In addition, we demonstrate a transient poisoning mechanism of the Ni SAC by nitrite and thiocyanate, explaining the recovery of activity during CO2RR.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"24 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435442","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}
Zhihui Chen, Qi Li, Huijun Tang, Junjie Wen, Yanyi Zhong, Jiangbin Zhang, Kai Han, Yao Liu
Electron transport properties of cathode interlayers are crucial to high‐performance organic solar cells (OSCs). We propose a novel approach to enhance electron transport of cathode interlayers through controlling a preferential face‐on molecular orientation of non‐ionic perylene‐diimide‐ (PDI) based cathode interlayers with restricted n‐doping effects. 1‐(2,5,8‐trioxadec‐10‐yl)‐1,2,3‐triazole (TOT) units as bulky and extended side chains were incorporated into brominated‐PDIs via click chemistry to yield PDIBr‐TOT. TOT side chains impart PDI‐based interlayers with a dominant face‐on orientation, meanwhile leading to a negligible doping effect due to their weak electron‐donating properties. Impressively, at a slight doping level, higher electron mobility is gained through efficient vertical charge transport channels built by preferred face‐on molecular orientations of PDIBr‐TOT, beating the results acquired through strong doping effects of traditional PDIBr‐N with an edge‐on orientation. Thus, PDIBr‐TOT can suppress exciton recombination and lower the surface energies for good contact with active layers, consequently leading to increases in fill factor and short‐circuit current. Integrating PDIBr‐TOT with various active layers, a remarkable efficiency of 19.52% is obtained. Moreover, device stability is enhanced by restrained doping effects. Modulating face‐on orientations of cathode interlayers prescribed here will encourage further innovative designs of high‐performance cathode interlayers towards OSC advances.
{"title":"Dominant Face‐On Oriented Perylene‐Diimide Interlayers for High‐Performance Organic Solar Cells","authors":"Zhihui Chen, Qi Li, Huijun Tang, Junjie Wen, Yanyi Zhong, Jiangbin Zhang, Kai Han, Yao Liu","doi":"10.1002/anie.202424502","DOIUrl":"https://doi.org/10.1002/anie.202424502","url":null,"abstract":"Electron transport properties of cathode interlayers are crucial to high‐performance organic solar cells (OSCs). We propose a novel approach to enhance electron transport of cathode interlayers through controlling a preferential face‐on molecular orientation of non‐ionic perylene‐diimide‐ (PDI) based cathode interlayers with restricted n‐doping effects. 1‐(2,5,8‐trioxadec‐10‐yl)‐1,2,3‐triazole (TOT) units as bulky and extended side chains were incorporated into brominated‐PDIs via click chemistry to yield PDIBr‐TOT. TOT side chains impart PDI‐based interlayers with a dominant face‐on orientation, meanwhile leading to a negligible doping effect due to their weak electron‐donating properties. Impressively, at a slight doping level, higher electron mobility is gained through efficient vertical charge transport channels built by preferred face‐on molecular orientations of PDIBr‐TOT, beating the results acquired through strong doping effects of traditional PDIBr‐N with an edge‐on orientation. Thus, PDIBr‐TOT can suppress exciton recombination and lower the surface energies for good contact with active layers, consequently leading to increases in fill factor and short‐circuit current. Integrating PDIBr‐TOT with various active layers, a remarkable efficiency of 19.52% is obtained. Moreover, device stability is enhanced by restrained doping effects. Modulating face‐on orientations of cathode interlayers prescribed here will encourage further innovative designs of high‐performance cathode interlayers towards OSC advances.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"24 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435440","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}
Matthew W. Halloran, Roxanne Naumann, Aanchal Jaisingh, Nathan A. Romero, Michael D. Burkart
Aromatic diisocyanates, invaluable commodity chemicals for polymer manufacturing, are produced annually on megaton scales from petroleum‐derived diamines via phosgenation. Existing routes toward renewable alternatives are sparse and limited by access to functionalized aromatic starting materials, such as terephthalates. Herein, we report the development of a robust route to renewable terephthalates and aromatic diisocyanates from D‐galactose via Eastwood olefination and Diels‐Alder cycloaddition, followed by a mild electrochemical decarboxylative aromatization. This process was developed and applied on gram‐scale to synthesize terephthalates, which were transformed into aromatic diisocyanates via Curtius rearrangement in flow. We demonstrate gram‐scale preparation of 1,4‐phenylene diisocyanate and 2,5‐toluene diisocyanate and formulation of these monomers to prepare fully renewable thermoplastic polyurethanes. Preparation of these renewable aromatic diisocyanates proceeds without the use of high‐pressure gases or costly transition‐metals and represents a novel route to fully renewable aromatic diisocyanates.
{"title":"Renewable Terephthalates and Aromatic Diisocyanates from Galactose","authors":"Matthew W. Halloran, Roxanne Naumann, Aanchal Jaisingh, Nathan A. Romero, Michael D. Burkart","doi":"10.1002/anie.202421540","DOIUrl":"https://doi.org/10.1002/anie.202421540","url":null,"abstract":"Aromatic diisocyanates, invaluable commodity chemicals for polymer manufacturing, are produced annually on megaton scales from petroleum‐derived diamines via phosgenation. Existing routes toward renewable alternatives are sparse and limited by access to functionalized aromatic starting materials, such as terephthalates. Herein, we report the development of a robust route to renewable terephthalates and aromatic diisocyanates from D‐galactose via Eastwood olefination and Diels‐Alder cycloaddition, followed by a mild electrochemical decarboxylative aromatization. This process was developed and applied on gram‐scale to synthesize terephthalates, which were transformed into aromatic diisocyanates via Curtius rearrangement in flow. We demonstrate gram‐scale preparation of 1,4‐phenylene diisocyanate and 2,5‐toluene diisocyanate and formulation of these monomers to prepare fully renewable thermoplastic polyurethanes. Preparation of these renewable aromatic diisocyanates proceeds without the use of high‐pressure gases or costly transition‐metals and represents a novel route to fully renewable aromatic diisocyanates.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435467","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}
Hoimin Jung, Jeonguk Kweon, Jong-Min Suh, Andrés Arribas, Dongwook Kim, Mi Hee Lim, Sukbok Chang
Herein, we report a photocatalytic platform to access transient nitrenoids by designing photo‐responsive neutral rhodium‐hydroxamate complexes. Combined experimental and computational mechanistic studies, including electron paramagnetic resonance (EPR) and mass spectrometric analysis, suggest that electrophilic Fischer‐type Rh‐acylnitrenoid intermediates could be generated via photoactivation of corresponding Rh‐hydroxamates via N‐O bond homolysis and redox event. Moreover, catalytic acylnitrenoid transfer was explored toward the amidation of various hydrocarbons, amines, and alcohols to furnish new N–C, N–N, and N–O bonds.
{"title":"Catalytic Amino Group Transfer Reactions Mediated by Photoinduced Nitrene Formation from Rhodium‐Hydroxamates","authors":"Hoimin Jung, Jeonguk Kweon, Jong-Min Suh, Andrés Arribas, Dongwook Kim, Mi Hee Lim, Sukbok Chang","doi":"10.1002/anie.202422461","DOIUrl":"https://doi.org/10.1002/anie.202422461","url":null,"abstract":"Herein, we report a photocatalytic platform to access transient nitrenoids by designing photo‐responsive neutral rhodium‐hydroxamate complexes. Combined experimental and computational mechanistic studies, including electron paramagnetic resonance (EPR) and mass spectrometric analysis, suggest that electrophilic Fischer‐type Rh‐acylnitrenoid intermediates could be generated via photoactivation of corresponding Rh‐hydroxamates via N‐O bond homolysis and redox event. Moreover, catalytic acylnitrenoid transfer was explored toward the amidation of various hydrocarbons, amines, and alcohols to furnish new N–C, N–N, and N–O bonds.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"11 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435441","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}
Jie Zhang, Haorui Zheng, Fengqian Chen, Zitao Wang, Hui Li, Fuxing Sun, Dan Zhao, Valentin Valtchev, Shilun Qiu, Qianrong Fang
High-connectivity 3D covalent organic frameworks (COFs) have garnered significant attention due to their structural complexity, stability, and potential for functional applications. However, the synthesis of 3D COFs using mixed high-nodal building units remains a substantial challenge. In this work, we introduce two novel 3D COFs, JUC-661 and JUC-662, which are constructed using a combination of D2h-symmetric 8-nodal and D3h-symmetric 6-nodal building blocks. These COFs feature an unprecedented [8+6]-c pdp net with rare mesoporous polyhedral cages (~3.9 nm). Remarkably, JUC-661 and JUC-662 exhibit outstanding separation capabilities, achieving adsorption selectivities of 4.3 and 5.9, respectively, for C2H2/CO2 (1/1, v/v) mixtures. Dynamic breakthrough experiments confirm their excellent separation capability, maintaining this performance even under conditions of 100% humidity. Monte Carlo simulations and DFT calculations indicate that the exceptional adsorption performance is attributed to the well-defined pore cavities of the COFs, with fluorination of the building unit further enhancing C2H2 selectivity through improved electrostatic and host-guest interactions. This study expands the structural diversity of COFs and highlights their potential for low-energy separation processes.
{"title":"High-Connectivity 3D Covalent Organic Frameworks with pdp Net for Efficient C2H2/CO2 Separation","authors":"Jie Zhang, Haorui Zheng, Fengqian Chen, Zitao Wang, Hui Li, Fuxing Sun, Dan Zhao, Valentin Valtchev, Shilun Qiu, Qianrong Fang","doi":"10.1002/anie.202500161","DOIUrl":"https://doi.org/10.1002/anie.202500161","url":null,"abstract":"High-connectivity 3D covalent organic frameworks (COFs) have garnered significant attention due to their structural complexity, stability, and potential for functional applications. However, the synthesis of 3D COFs using mixed high-nodal building units remains a substantial challenge. In this work, we introduce two novel 3D COFs, JUC-661 and JUC-662, which are constructed using a combination of D2h-symmetric 8-nodal and D3h-symmetric 6-nodal building blocks. These COFs feature an unprecedented [8+6]-c pdp net with rare mesoporous polyhedral cages (~3.9 nm). Remarkably, JUC-661 and JUC-662 exhibit outstanding separation capabilities, achieving adsorption selectivities of 4.3 and 5.9, respectively, for C2H2/CO2 (1/1, v/v) mixtures. Dynamic breakthrough experiments confirm their excellent separation capability, maintaining this performance even under conditions of 100% humidity. Monte Carlo simulations and DFT calculations indicate that the exceptional adsorption performance is attributed to the well-defined pore cavities of the COFs, with fluorination of the building unit further enhancing C2H2 selectivity through improved electrostatic and host-guest interactions. This study expands the structural diversity of COFs and highlights their potential for low-energy separation processes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"176 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435650","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}
Natural photosynthesis plays a vital role in the supply of energy and oxygen necessary for the survival of biological organisms. The current leading proposal of the O‐O bond formation in photosystem II suggests the coupling between the central μ‐oxo (O5) and the additional oxygenic ligand (Ox) of the manganese‐calcium oxide cofactor. However, the subsequent process through which molecular dioxygen is formed remains elusive. In this report, quantum chemical calculations reveal that the O2 process is initiated by the cleavage of the Mn‐O5 bond, without a preliminary conformational change of the peroxide [O5‐Ox]2‐ group. Subsequently, the [O5‐Ox] moiety is converted from the superoxide to the weakly bound quasi‐O2 where the Mn‐Ox bond is cleaved, and after a twist of the quasi‐O2 unit, the free O2 is ultimately released. Alternative pathways display significantly slower kinetics, due to the lower structural stabilities of the rate‐limiting transition states. The cause of the difference is associated with the Jahn‐Teller axial orientation and the local ring strain within the Mn cluster. These findings contribute to unravelling the complex mechanism in an important step of photosynthetic oxygen evolution for a deeper understanding of nature’s water oxidation catalysis.
{"title":"Quantum Chemical Understanding of the O2 Release Process from Nature’s Water Splitting Cofactor","authors":"Yu Guo, Lars Kloo, Licheng Sun","doi":"10.1002/anie.202421383","DOIUrl":"https://doi.org/10.1002/anie.202421383","url":null,"abstract":"Natural photosynthesis plays a vital role in the supply of energy and oxygen necessary for the survival of biological organisms. The current leading proposal of the O‐O bond formation in photosystem II suggests the coupling between the central μ‐oxo (O5) and the additional oxygenic ligand (Ox) of the manganese‐calcium oxide cofactor. However, the subsequent process through which molecular dioxygen is formed remains elusive. In this report, quantum chemical calculations reveal that the O2 process is initiated by the cleavage of the Mn‐O5 bond, without a preliminary conformational change of the peroxide [O5‐Ox]2‐ group. Subsequently, the [O5‐Ox] moiety is converted from the superoxide to the weakly bound quasi‐O2 where the Mn‐Ox bond is cleaved, and after a twist of the quasi‐O2 unit, the free O2 is ultimately released. Alternative pathways display significantly slower kinetics, due to the lower structural stabilities of the rate‐limiting transition states. The cause of the difference is associated with the Jahn‐Teller axial orientation and the local ring strain within the Mn cluster. These findings contribute to unravelling the complex mechanism in an important step of photosynthetic oxygen evolution for a deeper understanding of nature’s water oxidation catalysis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"28 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435296","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}
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