Angewandte Chemie最新文献_第9页

Advances in the Design of Photoactivatable Metallodrugs: Excited State Metallomics

Angewandte Chemie Pub Date : 2025-01-13 DOI: 10.1002/ange.202423335

Dr. Huayun Shi, Dr. Rafael C. Marchi, Prof. Peter J. Sadler

引用次数: 0

Strained Dehydro-[2,2]-paracyclophane Enabled Planar Chirality Construction and [2.2]Paracyclophane Functionalization

Angewandte Chemie Pub Date : 2025-01-13 DOI: 10.1002/ange.202420667

Xue Zhang, Yi Zhou, Zhi-Xiang Yu, Prof. Dr. Chen-Ho Tung, Prof. Dr. Zhenghu Xu

{"title":"Strained Dehydro-[2,2]-paracyclophane Enabled Planar Chirality Construction and [2.2]Paracyclophane Functionalization","authors":"Xue Zhang, Yi Zhou, Zhi-Xiang Yu, Prof. Dr. Chen-Ho Tung, Prof. Dr. Zhenghu Xu","doi":"10.1002/ange.202420667","DOIUrl":"https://doi.org/10.1002/ange.202420667","url":null,"abstract":"Planar chirality found tremendous use in many fields, such as chemistry, optics, and materials science. In particular, planar chiral [2.2]paracyclophanes (PCPs) are a type of structurally interesting and practically useful chiral compounds bearing unique electronic and photophysical properties and thus have been widely used in π-stacking polymers, organic luminescent materials, and as a valuable toolbox for developing chiral ligands or organocatalysts. However, the synthesis of chiral PCP derivatives remains a longstanding challenge. Current synthetic methods primarily rely on chiral preparative liquid chromatography separation or chemical and kinetic resolution reactions. Here, we report an enantioconvergent alkynylation of an in situ-formed dehydro-[2,2]-paracyclophane intermediate by asymmetric copper(I) catalysis. This approach enables the efficient synthesis of valuable planar chiral PCP building blocks and heterocycles with good yields and excellent enantioselectivity. The success of this reaction lies in the development of a practical route to access strained dehydro-[2,2]-paracyclophane intermediates, which can also be utilized in various strain-release nucleophilic or cycloaddition reactions to synthesize diverse functionalized PCPs. DFT calculations of this reaction suggest that the enantioselectivity is determined by the aryne complexation with chiral copper(I) acetylide and the subsequent insertion reaction.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475500","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Pyrrole-Fused Nanographene and its Edge-Perchlorinated Derivative Featuring a Corannulene Core and Five N-doped Heptagons

Angewandte Chemie Pub Date : 2025-01-12 DOI: 10.1002/ange.202420228

Xue-Peng Zhang, Zuo-Chang Chen, Han-Rui Tian, Wen-Xin Zhang, Si-Wei Ying, Peng Du, Bin-Wen Chen, Yang-Rong Yao, Yin-Fu Wu, Mei-Lin Zhang, Prof. Shun-Liu Deng, Prof. Qianyan Zhang, Prof. Su-Yuan Xie, Prof. Lan-Sun Zheng

{"title":"A Pyrrole-Fused Nanographene and its Edge-Perchlorinated Derivative Featuring a Corannulene Core and Five N-doped Heptagons","authors":"Xue-Peng Zhang, Zuo-Chang Chen, Han-Rui Tian, Wen-Xin Zhang, Si-Wei Ying, Peng Du, Bin-Wen Chen, Yang-Rong Yao, Yin-Fu Wu, Mei-Lin Zhang, Prof. Shun-Liu Deng, Prof. Qianyan Zhang, Prof. Su-Yuan Xie, Prof. Lan-Sun Zheng","doi":"10.1002/ange.202420228","DOIUrl":"https://doi.org/10.1002/ange.202420228","url":null,"abstract":"A pyrrole-fused analogue of warped nanographene, designated as deca-nitrogen doped ′WNG′ (azaWNG), was synthesized through the annular fusion of decapyrroylcorannulene. The resulting azaWNG exhibited extremely limited solubility in common organic solvents and was characterized solely by mass spectrometry. Theoretical calculations revealed that azaWNG has a sunflower-like molecular structure with electron-deficient corannulene as the core and electron-rich pyrrole as the petals, demonstrating a significantly narrower energy gap compared to all-carbon WNG. To improve its solubility and facilitate precise structural characterization, iodine monochloride was utilized for edge-perchlorination of azaWNG, enabling successful separation and purification of chlorinated azaWNG in solution phase. X-ray crystallography analysis unequivocally confirmed that edge-perchlorinated azaWNG contains 5 heptagons and 11 pentagons embedded within the warped π skeleton. Cyclic voltammetry measurements indicated that the first oxidation potential of azaWNG is −0.59 V, representing the lowest value reported for any previously studied aza-nanographene. Consequently, azaWNG can be readily oxidized by AgPF6 or even atmospheric oxygen to yield stable oxidation states, as corroborated by UV/Visible absorption spectroscopy; this behavior is attributed to the fusion of ten pyrroles around corannulene. This work marks the first instance of nitrogen doping in WNG (C80H30), underscoring the significant modification to electronic structure induced by such doping.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 7","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143380569","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Regularly Arranged Heterogeneous Pores in Gas Separation Membranes Constructed by Cocrystallization of Porous Organic Molecules

Angewandte Chemie Pub Date : 2025-01-12 DOI: 10.1002/ange.202420086

Saisai Yu, Siyuan Yang, Miao Yang, Ju Yang, Ziye Song, Dingyue Hu, Heng Ji, Zhe Jia, Prof. Ming Liu

{"title":"Regularly Arranged Heterogeneous Pores in Gas Separation Membranes Constructed by Cocrystallization of Porous Organic Molecules","authors":"Saisai Yu, Siyuan Yang, Miao Yang, Ju Yang, Ziye Song, Dingyue Hu, Heng Ji, Zhe Jia, Prof. Ming Liu","doi":"10.1002/ange.202420086","DOIUrl":"https://doi.org/10.1002/ange.202420086","url":null,"abstract":"Integrating two or more materials to construct membranes with heterogeneous pore structures is an effective strategy for enhancing separation performance. Regularly arranging these heterogeneous pores can significantly optimize the combined effect of the introduced components. Porous Organic Cages (POCs), an emerging subclass of porous materials composed of discrete molecules, assemble to form interconnected pores and exhibit permanent porosity in the solid state. A unique feature of POCs is their modularity, enabling a “mix and match” approach to create co-crystal structures driven by the intermolecular interactions. Herein, we adopted the cocrystallization strategy for fabricating gas separation membranes. We prepared membranes from a series of [4+6] imine cage pairs, which vary in cavity sizes and include cages with fluorescence properties. By optimizing the cocrystalization conditions, we successfully fabricated continuous, defect-free gas membranes, benefiting from chiral recognition interactions. By introducing regularly alternating small and large pores, we addressed challenges such as the trade-off between permeability and selectivity in gas separation membrane. Moreover, the cocrystallization strategy has been proven effective for other molecular systems besides POCs, such as macrocycles, for the preparation of co-crystal membranes. This method broadens the scope for fabricating high-performance gas separation membranes with ordered heterogeneous pores.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 7","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143380568","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Buffered Hydroxyl Radical for Photocatalytic Non-Oxidative Methane Coupling

Angewandte Chemie Pub Date : 2025-01-12 DOI: 10.1002/ange.202420606

Xueyuan Wang, Xueshang Xin, Dr. Lunqiao Xiong, Dr. Jianlong Yang, Tieou Wang, Prof. Yang Yang, Dr. Zhipeng Huang, Prof. Nengchao Luo, Prof. Junwang Tang, Prof. Feng Wang

{"title":"Buffered Hydroxyl Radical for Photocatalytic Non-Oxidative Methane Coupling","authors":"Xueyuan Wang, Xueshang Xin, Dr. Lunqiao Xiong, Dr. Jianlong Yang, Tieou Wang, Prof. Yang Yang, Dr. Zhipeng Huang, Prof. Nengchao Luo, Prof. Junwang Tang, Prof. Feng Wang","doi":"10.1002/ange.202420606","DOIUrl":"https://doi.org/10.1002/ange.202420606","url":null,"abstract":"Hydroxy radical (⋅OH) is a prestigious oxidant that allows the cleavage of strong chemical bonds of methane but is untamed, leading to over-oxidation of methane and waste of oxidants, especially at high methane conversion. Here, we managed to buffer ⋅OH in an aqueous solution of photo-irradiated Fe3+, where ⋅OH almost participates in methane oxidation. Due to the interaction between Fe3+ and SO42−, the electron transfer from OH− to excited-state Fe3+ for ⋅OH generation is retarded, while excessive ⋅OH is consumed by generated Fe2+ to restore Fe3+. When combined with a Ru/SrTiO3:Rh photocatalyst, the buffered ⋅OH converts methane to C2+ hydrocarbons and H2 with formation rates of 246 and 418 μmol h−1, respectively. The apparent quantum efficiency reaches 13.0±0.2 %, along with 10.2 % methane conversion and 81 % C2+ selectivity after 80 hours of reaction. Overall, this work presents a strategy for controlling active radicals for selective and efficient photocatalysis.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Boosting One- and Two-Photon Excited Fluorescence of Interpenetrated Tetraphenylethene-Based Metal–Organic Frameworks (TPE-MOFs) by Linker Installation

Angewandte Chemie Pub Date : 2025-01-12 DOI: 10.1002/ange.202420912

Huihui He, Ji Li, Jiayi Zhuang, Jinyi Huang, Yuxuan Meng, Xi Lin, Prof. Dr. Zhangwen Wei, Prof. Dr. Liangliang Zhang, Prof. Dr. Yu Fang, Prof. Dr. Mei Pan

{"title":"Boosting One- and Two-Photon Excited Fluorescence of Interpenetrated Tetraphenylethene-Based Metal–Organic Frameworks (TPE-MOFs) by Linker Installation","authors":"Huihui He, Ji Li, Jiayi Zhuang, Jinyi Huang, Yuxuan Meng, Xi Lin, Prof. Dr. Zhangwen Wei, Prof. Dr. Liangliang Zhang, Prof. Dr. Yu Fang, Prof. Dr. Mei Pan","doi":"10.1002/ange.202420912","DOIUrl":"https://doi.org/10.1002/ange.202420912","url":null,"abstract":"Immobilizing organic chromophores within the rigid framework of metal-organic frameworks (MOFs) augments fluorescence by effectively curtailing molecular motions. Yet, the substantial interspaces and free volumes inherent to MOFs can undermine photoluminescence efficiency, as they partially constrain intramolecular dynamics. In this study, we achieved optimization of both one- and two-photon excited fluorescence by incorporating linkers into an interpenetrated tetraphenylethene-based MOF (TPE-MOF). This linker installation strategy enables fine-tuning of both crystal packing density and ligand conformations. Strikingly, the desolvated MOFs exhibit remarkable two-photon absorption (TPA) cross-sections, reaching an impressive 8801 GM. Consequently, these materials demonstrate exceptional performance in one- and two-photon excited cellular imaging of HepG2 cells. Our work introduces an innovative approach to enhancing two-photon excited fluorescence (TPEF) and broadens the scope of research into one- and two-photon excited fluorescence (1/2 PEF).","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Frontispiz: Photo-Triggered Fluorescence Polyelectrolyte Nanoassemblies: Manipulate and Boost Singlet Oxygen in Photodynamic Therapy

Angewandte Chemie Pub Date : 2025-01-11 DOI: 10.1002/ange.202580261

Dr. Yongkang Yao, Dr. Shangjun Chen, Dr. Chenxu Yan, Prof. Dr. Junyou Wang, Prof. Dr. Jianjun Liu, Prof. Dr. Wei-Hong Zhu, Prof. Dr. Chunhai Fan, Prof. Dr. Zhiqian Guo

引用次数: 0

Frontispiz: A Double-walled Noncovalent Carbon Nanotube by Columnar Packing of Nanotube Fragments

Angewandte Chemie Pub Date : 2025-01-11 DOI: 10.1002/ange.202580262

Daiki Imoto, Dr. Hiroki Shudo, Prof. Dr. Akiko Yagi, Prof. Dr. Kenichiro Itami

引用次数: 0

Aryl-Acetylen-Schichthybrid-Perowskite in der Photovoltaik

Angewandte Chemie Pub Date : 2025-01-11 DOI: 10.1002/ange.202417432

Ghewa AlSabeh, Dr. Vladislav Slama, Ming Ren, Dr. Masaud Almalki, Dr. Lukas Pfeifer, Prof. Dr. Dominik J. Kubicki, Paul Zimmermann, Dr. Alexander Hinderhofer, Fabiola Faini, Dr. Davide Moia, Mostafa Othman, Dr. Felix T. Eickemeyer, Dr. Virginia Carnevali, Dr. Nikolaos Lempesis, Dr. Andrea Vezzosi, Dr. Fatemeh Ansari, Prof. Frank Schreiber, Prof. Joachim Maier, Dr. Christian M. Wolff, Dr. Aïcha Hessler-Wyser, Prof. Christophe Ballif, Prof. Giulia Grancini, Prof. Ursula Rothlisberger, Prof. Michael Grätzel, Prof. Jovana V. Milić

{"title":"Aryl-Acetylen-Schichthybrid-Perowskite in der Photovoltaik","authors":"Ghewa AlSabeh, Dr. Vladislav Slama, Ming Ren, Dr. Masaud Almalki, Dr. Lukas Pfeifer, Prof. Dr. Dominik J. Kubicki, Paul Zimmermann, Dr. Alexander Hinderhofer, Fabiola Faini, Dr. Davide Moia, Mostafa Othman, Dr. Felix T. Eickemeyer, Dr. Virginia Carnevali, Dr. Nikolaos Lempesis, Dr. Andrea Vezzosi, Dr. Fatemeh Ansari, Prof. Frank Schreiber, Prof. Joachim Maier, Dr. Christian M. Wolff, Dr. Aïcha Hessler-Wyser, Prof. Christophe Ballif, Prof. Giulia Grancini, Prof. Ursula Rothlisberger, Prof. Michael Grätzel, Prof. Jovana V. Milić","doi":"10.1002/ange.202417432","DOIUrl":"https://doi.org/10.1002/ange.202417432","url":null,"abstract":"Metallhalogenid-Perowskite haben ein außerordentliches Potenzial für die Umwandlung von Sonnenenergie in elektrische Energie in der Photovoltaik gezeigt, doch ihre Anwendung wird durch eine begrenzte Betriebsstabilität behindert. Dies hat die Entwicklung hybrider, geschichteter (zweidimensionaler, 2D) Halogenid-Perowskite auf der Grundlage hydrophober organischer Spacer (Abstandshalter) angeregt, die Perowskit-Schichten als stabilere Alternative ermöglichen. Herkömmliche organische Spacer-Kationen sind jedoch elektronisch isolierend, was zu einem Ladungseinschluss innerhalb der anorganischen Schichten führt und damit deren Funktionalität einschränkt. Dies kann durch die Erweiterung der π-Konjugation der Spacer-Kationen verbessert werden. Wir zeigen, dass wir Zugang zu Ruddlesden-Popper- und Dion-Jacobson-2D-Perowskiten haben, die zum ersten Mal Aryl-Acetylen-basierte (4-Ethinylphenyl)methylammonium- (BMAA) bzw. Buta-1,3-Din-1,4-diylbis(4,1-phenylen)dimethylammonium- (BDAA) Spacer enthalten. Wir bewerten ihre einzigartigen opto(elektro)ionischen Eigenschaften durch eine Kombination von Techniken und wenden sie in gemischtdimensionalen Perowskit-Solarzellen an, die eine überragende Leistung mit einem Wirkungsgrad von bis zu 23 % und eine höhere Betriebsstabilität aufweisen, was den Weg für Multifunktionalität in geschichteten Hybridmaterialien und deren Anwendung öffnet.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Dynamic Phosphorescence Behavior of Carbene-Metal-Amide Complexes from the Perspective of Excited State Modulation

Angewandte Chemie Pub Date : 2025-01-10 DOI: 10.1002/ange.202419614

Xiang-Ming Zeng, Minjian Wu, Prof. Dr. Liao-Yuan Yao, Prof. Dr. Guo-Yu Yang

{"title":"Dynamic Phosphorescence Behavior of Carbene-Metal-Amide Complexes from the Perspective of Excited State Modulation","authors":"Xiang-Ming Zeng, Minjian Wu, Prof. Dr. Liao-Yuan Yao, Prof. Dr. Guo-Yu Yang","doi":"10.1002/ange.202419614","DOIUrl":"https://doi.org/10.1002/ange.202419614","url":null,"abstract":"Carbene-metal-amide (CMA) complexes have diverse applications in luminescence, imaging and sensing. In this study, we designed and synthesized a series of CMA complexes, which were subsequently doped into a PMMA host. These materials demonstrate light-induced dynamic phosphorescence, attributed to their long intrinsic triplet state lifetime (τP,int, in the μs-ms scale), high intersystem crossing (ISC) rate constant (kISC, up to 107 s−1), and bright phosphorescence. The extended τP,int, and elevated kISC facilitate efficient sensitization of singlet oxygen (1O2) under light irradiation, which is rapidly consumed by the host material, creating a localized anaerobic environment conducive to bright phosphorescence emission. The Sn-T1 process exhibits a large spin-orbital coupling matrix element (SOCME) value, while the SOCME value between T1 and S0 is comparatively smaller, resulting in a large kISC and long τP,int, Computational results indicate that the hole-electron configuration in the lowest triplet state exhibits low contributions from gold. Based on the dynamic phosphorescence properties, an encryption material capable of achieving a “burn after reading” effect was developed. This work illustrates that those phosphorescent emitters with minimal heavy atom contribution can produce dynamic phosphorescent phenomena, providing a novel strategy for designing stimuli-responsive phosphorescent materials.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 7","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143380680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0