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Discovery of (±)-Penindolenes Reveals an Unusual Indole Ring Cleavage Pathway Catalyzed by P450 Monooxygenase Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-18 Ling-Hong Meng, Takayoshi Awakawa, Xiao-Ming Li, Zhiyang Quan, Sui-Qun Yang, Bin-Gui Wang, Ikuro Abe
(±)-Penindolenes A–D (1–4), the first representatives of indole terpenoids featuring a γ-lactam skeleton, were isolated from the mangrove-derived endophytic fungus Penicillium brocae MA-231. Our bioactivity tests revealed their potent antimicrobial and acetylcholinesterase inhibitory activities. The biosynthetic reactions by the five enzymes PbaABCDE leading to γ-lactam ring formation were identified
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Formation of Supernarrow Borophene Nanoribbons Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Haochen Wang, Pengcheng Ding, Guang-Jie Xia, Xiangyun Zhao, Wenlong E, Miao Yu, Zhibo Ma, Yang-Gang Wang, Lai-Sheng Wang, Jun Li, Xueming Yang
Borophenes have sparked considerable interest owing to their fascinating physical characteristics and diverse polymorphism. However, borophene nanoribbons (BNRs) with widths less than 2 nm have not been achieved. Herein, we report the experimental realization of supernarrow BNRs. Combining scanning tunneling microscopy imaging with density functional theory modeling and ab initio molecular dynamics
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Facile generation of heterotelechelic poly(2‐oxazoline)s towards accelerated exploration of poly(2‐oxazoline)‐based nanomedicine Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Joachim F. R. Van Guyse, Saed Abbasi, Kazuko Toh, Zlata Nagorna, Junjie Li, Anjaneyulu Dirisala, Sabina Quader, Satoshi Uchida, Kazunori Kataoka
Controlling the end‐groups of biocompatible polymers is crucial for enabling polymer‐based therapeutics and nanomedicine. Typically, end‐group diversification is a challenging and time‐consuming endeavor, especially for polymers pre‐pared via ionic polymerization mechanisms with limited functional group tolerance. In this study, we present a facile end‐group diversification approach for poly(2‐oxazoline)s
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Discovery, Structure, and Engineering of a cis‐Geranylfarnesyl Diphosphate Synthase Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Fang-Ru Li, Qingling Wang, Xingming Pan, Hui-Min Xu, Liao-Bin Dong
cis‐Prenyltransferases (cis‐PTs) catalyze the sequential head‐to‐tail condensation of isopentenyl diphosphate (IPP) to allylic diphosphates, producing mixed E‐Z prenyl diphosphates of varying lengths; yet, the specific enzymes synthesizing cis‐C25 prenyl diphosphates have not been identified. In this study, we present the discovery and characterization of a cis‐geranylfarnesyl diphosphate synthase
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Electrochemical Synthesis of C(sp3)‐Rich Amines by Aminative Carbofunctionalization of Carbonyl Compounds Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Wen-Qiang Liu, Boon Chong Lee, NingXi Song, Zhenghao He, Zi-An Shen, Yixin Lu, Ming Joo Koh
Alkylamines form the backbone of countless nitrogen‐containing small molecules possessing desirable biological properties. Despite advances in amine synthesis through transition metal catalysis and photoredox chemistry, multicomponent reactions that leverage inexpensive materials to transform abundant chemical feedstocks into three‐dimensional α‐substituted alkylamines bearing complex substitution
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A New Family of High Oxidation State Antiperovskite Nitrides: La3MN5 (M = Cr, Mn and Mo) Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Yao Yuan, Minghui Yang, Simon D. Kloß, John Paul Attfield
Three new nitrides La3MN5 (M = Cr, Mn, and Mo) have been synthesized using a high pressure azide route. These are the first examples of ternary Cs3CoCl5‐type nitrides, and show that this (MN4)NLa3 antiperovskite structure type may be used to stabilise high oxidation‐state transition metals in tetrahedral molecular [MN4]n‐ nitridometallate anions. Magnetic measurements confirm that Cr and Mo are in
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Nickel‐Catalyzed Chemoselective Carbomagnesiation for Atroposelective Ring‐Opening Difunctionalization Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Tingting Sun, Linchao Guo, Qi Li, Zhi-Chao Cao
There is a pressing need for methods that can connect enantioenriched organic compounds with readily accessible building blocks via asymmetric functionalization of unreactive chemical bonds in organic synthesis and medicinal chemistry. Herein, the asymmetric chemoselective cleavage of two unactivated C(Ar)‐O bonds in the same molecule is disclosed for the first time through an unusual nickel‐catalyzed
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Acceptor‐Reactivity‐Controlled Stereoconvergent Synthesis and Immunological Activity of a Unique Pentasaccharide from the Cell Wall Polysaccharide of Cutibacterium acnes C7 Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Tianhui Hao, Ke Feng, Hongzhen Jin, Jiawei Li, Chenkai Zhou, Xingbang Liu, Wei Zhao, Fan Yu, Tiehai Li
Bacterial cell‐surface polysaccharides are involved in various biological processes and have attracted widespread attention as potential targets for developing carbohydrate‐based drugs. However, the accessibility of structurally well‐defined polysaccharide or related active oligosaccharide domains remains challenging. Herein, we describe an efficiently stereocontrolled approach for the first total
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Noncovalent Interaction Guided Precise Photoluminescence Regulation of Gold Nanoclusters in Both Isolate Species and Aggregate States Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Xiaoxi Luo, Jie Kong, Hang Xiao, Dongmiao Sang, Kui He, Meng Zhou, Jinbin Liu
Designing luminophores bright in both isolate species and aggregate states is of great importance in many emerging cutting‐edge applications. However, the conventional luminophores either emit in isolate species but quench in aggregate state or emit in aggregate state but darken in isolate species. Here we demonstrate that the precise regulation of noncovalent interactions can realize luminophores
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Discovery of Alloy Catalysts Beyond Pd for Selective Hydrogenation of Reformate via First‐principle Screening with Consideration of H‐coverage Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 jiayi wang, haoxiang xu, Yihao Zhang, jianguo wu, haowen ma, xuecheng zhan, jiqin zhu, Daojian Cheng
The highly selective hydrogenation to remove olefins is a significant refining approach for the reformate. Herein, a library of transition metal for reformate hydrogenation is tested experimentally to validate the predictive level of catalytic activity from our theoretical framework, which combines ab initio calculations and microkinetic modeling, with consideration of surface H‐coverage effect on
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Enrooted‐type metal‐support interaction boosting oxygen evolution reaction in acidic media Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Wenjuan Wang, Cheng Li, Chuan Zhou, Xin Xiao, Fayan Li, Ning-yu Huang, Lei Li, Meng Danny Gu, Qiang Xu
Supported metal catalysts with appropriate metal‐support interactions (MSIs) hold a great promise for heterogeneous catalysis. However, ensuring tight immobilization of metal clusters/nanoparticles on the support while maximizing the exposure of surface active sites remains a huge challenge. Herein, we report an Ir/WO3 catalyst with a new enrooted‐type MSI in which Ir clusters are, unprecedentedly
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Polyfluorinated Organic Diammonium Induced Lead Iodide Arrangement for Efficient Two‐Step‐Processed Perovskite Solar Cells Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Yang liu, Qiuju Liu, Lu Yusong, Jianfei Fu, Jifeng Wu, Yan Zhang, Qingyong Tian, Bin Fan, Hua Bai, Hai-Qiao Wang
The inefficient conversion of lead iodide to perovskite has become one of the major challenges in further improving the performance of perovskite solar cells fabricated by the two‐step method. Herein, the discontinuous lead iodide layer realized by introduction of a polyfluorinated organic diammonium salt, octafluoro‐([1,1′‐biphenyl]‐4,4′‐diyl)‐dimethanaminium (OFPP) iodide which does not form low‐dimensional
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Adhesion Peptide‐Functionalized Biobased Microgels for Controlled Delivery of Pesticides Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Abdulkadir Yayci, Tim Sassmann, Alexander Boes, Felix Jakob, Alexander Töpel, Anne Loreth, Carolin Rauch, Andrij Pich, Ulrich Schwaneberg
Widespread use of plant protection agents in agriculture is a major cause of pollution. Apart from active ingredients, the environmental impact of auxiliary synthetic polymers should be minimized if they are highly persistent. An alternative to synthetic polymers is the use of natural polysaccharides, which are abundant and biodegradable. In this study, we explore pectin microgels functionalized with
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Cathodic Deposition‐Assisted Synthesis of Thin Glass MOF Films for High‐Performance Gas Separations Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Sijie Xie, Xiaoyu Tan, Zhenhong Xue, Pieter Geysens, Hui Pan, Wei Guo, Zhenyu Zhou, Xuan Zhang, Ivo F.J. Vankelecom, Jan Fransaer
Glass metal‐organic framework (MOF) films can be fabricated from their crystalline counterparts through a melt‐quenching process and are prospective candidates for gas separation because of the elimination of the grain boundaries in crystalline MOF films. However, current techniques are limited to producing glass MOF films with a thickness of tens of micrometers, which leads to ultralow gas permeances
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High‐Pressure‐Field Induced Synthesis of Ultrafine‐Sized High‐Entropy Compounds with Excellent Sodium‐Ion Storage Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Ming Liang, Haonan Xie, biao chen, Hongye Qin, Hanwen Zhang, Jingyi Wang, Junwei Sha, Liying Ma, Enzuo Liu, Jianli Kang, Chunsheng Shi, Fang He, Xiaopeng Han, Wenbin Hu, Naiqin Zhao, Chunnian He
Emerging high entropy compounds (HECs) have attracted huge attention in electrochemical energy‐related applications. The features of ultrafine size and carbon incorporation show great potential to boost the ion‐storage kinetics of HECs. However, they are rarely reported because high‐temperature calcination tends to result in larger crystallites, phase separation, and carbon reduction. Herein, using
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Cover Picture: Droplet‐Based Microfluidics Reveals Insights into Cross‐Coupling Mechanisms over Single‐Atom Heterogeneous Catalysts Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Thomas Moragues, Georgios Giannakakis, Andrea Ruiz‐Ferrando, Camelia N. Borca, Thomas Huthwelker, Aram Bugaev, Andrew J. de Mello, Javier Pérez‐Ramírez, Sharon Mitchell
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Cover Picture: Hydrogen‐Bond‐Network Breakdown Boosts Selective CO2 Photoreduction by Suppressing H2 Evolution Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Die Cong, Jikai Sun, Yuwei Pan, Xu Fang, Li Yang, Wei Zhou, Tie Yu, Zhen Li, Chengcheng Liu, Wei‐Qiao Deng
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Synergistic Effect of Ni/Ni(OH)2 Core‐Shell Catalyst Boosts Tandem Nitrate Reduction for Ampere‐Level Ammonia Production Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Xinyue Shi, Minghui Xie, Kaiwen Yang, Yutao Niu, Haibin Ma, Yiming Zhu, Jiayi Li, Tingting Pan, Xiaoyan Zhou, Yujie Cui, Zhao Li, Yifu Yu, Xiaohua Yu, Jiwei Ma, Hongfei CHENG
Electrocatalytic reduction of nitrate to ammonia provides a green alternate to the Haber‐Bosch method, yet it suffers from sluggish kinetics and a low yield rate. The nitrate reduction follows a tandem reaction of nitrate reduction to nitrite and subsequent nitrite hydrogenation to generate ammonia, and the ammonia Faraday efficiency (FE) is limited by the competitive hydrogen evolution reaction. Herein
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Back Cover: Abiotic Methane Production Driven by Ubiquitous Non‐Fenton‐Type Reactive Oxygen Species Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Jie Ye, Andong Hu, Chao Gao, Fengqi Li, Lei Li, Yulin Guo, Guoping Ren, Bing Li, Christopher Rensing, Kenneth H. Nealson, Shungui Zhou, Yujie Xiong
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Single‐Atom Iron Catalyst as an Advanced Redox Mediator for Anodic Oxidation of Organic Electrosynthesis Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Xin-Yu Wang, Yong-Zhou Pan, Jiarui Yang, Wen-Hao Li, Tao Gan, Ying-Ming Pan, Hai-Tao Tang, Dingsheng Wang
Homogeneous electrocatalysts can indirect oxidate the high overpotential substrates through single‐electron transfer on the electrode surface, enabling efficient operation of organic electrosynthesis catalytic cycles. However, the problems of this chemistry still exist such as high dosage, difficult recovery, and low catalytic efficiency. Single‐atom catalysts (SACs) exhibit high atom utilization and
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Coral ‐Inspired Terahertz–Infrared Bi‐Stealth Electronic Skin Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-23 Shangjing Li, Kaichao Pan, Jiang Du, Zunfeng Liu, Jun Qiu
The development of electronic skin with dual stealth functionality is crucial for enabling devices to operate effectively in dynamic electromagnetic environments, thereby facilitating intelligent electromagnetic protection for autonomous perception. However, achieving compatibility between terahertz (THz) and infrared (IR) stealth technologies remains largely unexplored due to their inherent contradictions
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A Dicopper(II)-Based Carbonic Anhydrase Model - Quantum-Chemical Evaluation of the Mechanistic Pathway Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-17 Peter Comba, Gunasekaran Velmurugan, Philipp Baur
The cyanobacterium Prochloron didemni, an obligate symbiont of different species of colonial ascidians, occurring in the Pacific and Indian Oceans, produces a variety of cyclic peptides. These patellamide-type macrocycles lead to relatively stable dicopper(II) complexes that are extremely efficient carbonic anhydrase mimics, the most active model systems known so far. Importantly, it recently was shown
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Perfluorooxosulfate Salts as SOF4-Gas-Free Precursors to Multidimensional SuFEx Electrophiles Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-17 Armir Zogu, Karim Ullah, Stefanos Spanopoulos, Ermal Ismalaj, Wim M. De Borggraeve, Joachim Demaerel
Sulfur(VI) Fluoride Exchange (SuFEx) chemistry stands as a well-established method for swiftly constructing complex molecules in a modular fashion. An especially promising segment of this toolbox is reserved for multidimensional SuFEx hubs: three or more substituents pluggable into a singular SVI centre to make ‘beyondlinear’ clicked constructions. Sulfurimidoyl difluorides (RNSOF2) stand out as the
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Neuron‐Like Silicone Nanofilaments@Montmorillonite Nanofillers of PEO‐Based Solid‐State Electrolytes for Lithium Metal Batteries with Wide Operation Temperature Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Wankai Wang, Yanfei Yang, Jie Yang, Junping Zhang
Poly(ethylene oxide) (PEO)‐based composite solid electrolytes (CSEs) are promising to accelerate commercialization of solid‐state lithium metal batteries (SSLMBs). Nonetheless, this is hindered by the CSEs' limited ion conductivity at room temperature. Here, we propose design, synthesis, and application of the bioinspired neuron‐like nanofillers for PEO‐based CSEs. The neuron‐like superhydrophobic
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Insights into the Distinct Behaviors between Bifunctional and Binary Organoborane Catalysts through Terpolymerization of Epoxide, CO2, and Anhydride Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Rui Xie, Yuhui Wang, Shuai Li, Bo Li, Jie Xu, Jinqian Liu, Yuchen He, Guan-Wen Yang, Guang-Peng Wu
Alkyl borane compounds‐mediated polymerizations have expanded to Lewis pair polymerization, free radical polymerization, ionic ring‐opening polymerization, and polyhomologation. The bifunctional organoborane catalysts that contain the Lewis acid and ammonium or phosphonium salt in one molecule have demonstrated superior catalytic performance for ring‐opening polymerization of epoxides and ring‐opening
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Enhancing Built‐in Electric Fields via Molecular Symmetry Modulation in Supramolecular Photocatalysts for Highly Efficient Photocatalytic Hydrogen Evolution Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Xiaolin Zhu, Yihui Jia, Yuhan Liu, Jingyi Xu, Huarui He, Siyue Wang, Yang Shao, Yaxin Zhai, Yongfa Zhu
Nature‐inspired supramolecular self‐assemblies are attractive photocatalysts, but their quantum yields are limited by poor charge separation and transportation. A promising strategy for efficient charge transfer is to enhance the built‐in electric field by symmetry breaking. Herein, an unsymmetric protonation, N‐heterocyclic π‐conjugated anthrazoline‐based supramolecular photocatalyst SA‐DADK‐H+ was
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An Electrocatalytic Cascade Reaction for the Synthesis of Ketones Using CO2 as a CO Surrogate Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Ahmed M. Sheta, Sergio Fernández, Changwei Liu, Geyla C. Dubed‐Bandomo, Julio Lloret‐Fillol
The construction of carbonyl compounds via carbonylation reactions using safe CO sources remains a long‐standing challenge to synthetic chemists. Herein, we propose a catalyst cascade Scheme in which CO2 is used as a CO surrogate in the carbonylation of benzyl chlorides. Our approach is based on the cooperation between two coexisting catalytic cycles: the CO2‐to‐CO electroreduction cycle promoted by
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Controlled Synthesis of Unconventional Phase Alloy Nanobranches for Highly Selective Electrocatalytic Nitrite Reduction to Ammonia Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Yunhao Wang, Yuecheng Xiong, Mingzi Sun, Jingwen Zhou, Fengkun Hao, Qinghua Zhang, Chenliang Ye, Xixi Wang, Zhihang Xu, Qingbo Wa, Fu Liu, Xiang Meng, Juan Wang, Pengyi Lu, Yangbo Ma, Jinwen Yin, Ye Zhu, Shengqi Chu, Bolong Huang, Lin Gu, Zhanxi Fan
The controlled synthesis of metal nanomaterials with unconventional phases is of significant importance to develop high‐performance catalysts for various applications. However, it remains challenging to modulate the atomic arrangements of metal nanomaterials, especially the alloy nanostructures that involve different metals with distinct redox potentials. Here we report the general one‐pot synthesis
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Lithium Pre‐Storage Enables High Initial Coulombic Efficiency and Stable Lithium‐Enriched Silicon/Graphite Anode Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Yingjie Gao, Chenghao Cui, Zhikun Huang, Guoyu Pan, Yuanfan Gu, Yanan Yang, Fan Bai, Zhuang Sun, Tao Zhang
Application of silicon‐based anode is significantly challenged by low initial Coulombic efficiency (ICE) and poor cyclability. Traditional pre‐lithiation reagents often pose safety concerns due to their unstable chemical nature. Achieving a balance between water‐stability and high ICE in prelithiated silicon is a critical issue. Here, we present a lithium‐enriched silicon/graphite material with an
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Translocation and confinement of tetraamines in adaptable microporous cavities Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Ana Rubio-Gaspar, Alechania Misturini, Reisel Millán, Neyvis Almora-Barrios, Sergio Tatay, Volodymyr Bon, Mickaele Bonneau, Vincent Guillerm, Mohamed Eddaoudi, Sergio Navalón, Stefan Kaskel, Donatella Armentano, Carlos Marti-Gastaldo
Metal‐Organic Frameworks can be grafted with amines by coordination to metal vacancies to create amine‐appended solid adsorbents, which are being considered as an alternative to using aqueous amine solutions for CO2 capture. In this study, we propose an alternative mechanism that does not rely on the use of neutral metal vacancies as binding sites but is enabled by the structural adaptability of heterobimetallic
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Electrochemically Mediated Atom Transfer Radical Polymerization Driven by Alternating Current Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Francesco De Bon, Marco Fantin, Vanessa A. Pereira, Teresa J. Lourenço Bernardino, Armenio Coimbra Serra, Krzysztof Matyjaszewski, Jorge Fernando Jordao Coelho
Alternating current (AC) and pulsed electrolysis are gaining traction in electro(organic) synthesis due to their advantageous characteristics. We employed AC electrolysis in electrochemically mediated Atom Transfer Radical Polymerization (eATRP) to facilitate the regeneration of the activator CuI complex on Cu0 electrodes. Additionally, Cu0 served as a slow supplemental activator and reducing agent
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Dual Redox Reaction Sites for Pseudocapacitance Based on Ti and ‐P Functional Groups of Ti3C2PBrx MXene Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Jiamin Zhu, Shengli Zhu, Zhenduo Cui, Zhaoyang Li, Shuilin Wu, Wence Xu, Zhonghui Gao, Te Ba, Chunyong Liang, Yanqin Liang, Hui Jiang
MXenes have extensive applications due to their different properties determined by intrinsic structures and various functional groups. Exploring different functional groups of MXenes leads to improved performance or potential applications. In this work, we prepared new Ti3C2PBrx (x=0.4‐0.6) MXene with phosphorus functional groups (‐P) through a two‐step gas‐phase reaction. The acquisition of ‐P is
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Boron‐Catalyzed C1 Copolymerization of Arsonium and Sulfoxonium Ylidestoward Unrepresented Structures and Fluorescence Properties Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Mingtao Zhou, Nikos Hadjichristidis
The first synthesis of well‐defined poly(methylene‐co‐1,1‐diphenylpropenenylene) (C1‐co‐C1’), equivalent to poly(ethylene‐co‐diphenylbutadiene) copolymer was accomplished by C1 copolymerization of novel diphenylpropenyl triphenyl arsonium ylides (Ph2AY) and dimethylsulfoxonium methylide (Me2SY) using B‐thexylborepane as an initiator. All polymerization conditions, including feed ratio, temperature
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Detection of Sulfoquinovosidase Activity in Cell Lysates Using Activity‐Based Probes Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Zirui Li, Isabelle Pickles, Mahima Sharma, Benjamin Melling, Jeroen Codee, Luise Pallasdies, Spencer Williams, Herman Overkleeft, Gideon John Davies
The sulfolipid sulfoquinovosyl diacylglycerol (SQDG), produced by plants, algae, and cyanobacteria, constitutes a major sulfur reserve in the biosphere. Microbial breakdown of SQDG is critical for the biological utilization of its sulfur. This commences through release of the parent sugar, sulfoquinovose (SQ), catalyzed by sulfoquinovosidases (SQases). These vanguard enzymes are encoded in gene clusters
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Micelles Cascade Assembly to Tandem Porous Catalyst for Waste Plastics Upcycling Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Jiayou Feng, Jindi Duan, Chin-Te Hung, Zhenghao Zhang, Kailin Li, Yan Ai, Chaochao Yang, Yiyue Zhao, Zhengmin Yu, Yahong Zhang, Liang Wang, Dongyuan Zhao, Wei Li
Catalytic upcycling of polyolefins into high‐value chemicals represents the direction in end‐of‐life plastics valorization, but poses great challenges. Here, we report the synthesis of a tandem porous catalyst via a micelle cascade assembly strategy for selectively catalytic cracking of polyethylene into olefins at a low temperature. A hierarchically porous silica layer from mesopore to macropore is
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Blocking Interfacial Proton Transport via Self‐Assembled Monolayer for Hydrogen Evolution‐Free Zinc Batteries Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Jianping Chen, Yayun Shi, Songhe Zheng, Wanyu Zhao, Ruimin Li, Ke Ye, Xiaoli Zhao, Zhijun Zuo, Zhenghui Pan, Xiaowei Yang
Aqueous Zn‐ion batteries (ZIBs) are promising next‐generation energy storage devices, yet suffer from the issues of hydrogen evolution reaction (HER) and intricate side reactions on the Zn anode surface. The hydrogen (H)‐bond networks play a critical role in interfacial proton transport that may closely relate to HER but are rarely investigated.Herein, we report a self‐assembled monolayer (SAM) strategy
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A Carbon‐Caged Rhodamine Generating Nitrosoperoxycarbonate for Photoimmunotherapy Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Lei Yin, Bei Zhao, Jie Zhou, Yunxia Huang, Hao Ma, Ting Zhou, Jie Mou, Peiru Min, Jinquan Chen, Guangbo Ge, Xuhong Qian, Xiao Luo, Youjun Yang
Photoimmunotherapy is a promising cancer treatment modality. While potent 1‐e‐ oxidative species are known to induce immunogenic cell death (ICD), they are also associated with unspecific oxidation and collateral tissue damage. This difficulty may be addressed by post‐generation radical reinforcement. Namely, non‐oxidative radicals are first generated and subsequently activated into powerful oxidative
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Single Crystal and Pentatwinned Gold Nanorods Result in Chiral Nanocrystals with Reverse Handedness Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Kyle Van Gordon, Bing Ni, Robin Girod, Mikhail Mychinko, Francisco Bevilacqua, Sara Bals, Luis M Liz-Marzán
Handedness is an essential attribute of chiral nanocrystals, having a major influence on their properties. During chemical growth, the handedness of nanocrystals is usually tuned by selecting the corresponding enantiomer of chiral molecules involved in asymmetric growth, often known as chiral inducers. We report that, even using the same chiral inducer enantiomer, the handedness of chiral gold nanocrystals
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Oxygen Vacancies Boosted Hydronium Intercalation: A Paradigm Shift in Aluminum‐based Batteries Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Chengxiang Huang, Zhou Jiang, Fuxi Liu, Wenwen Li, Qing Liang, Zhenzhen Zhao, Xin Ge, Kexin Song, Lirong Zheng, Xin Zhou, Sifan Qiao, Wei Zhang, Weitao Zheng
In aqueous aluminum‐ion batteries(AAIBs), the insertion/extraction chemistry of Al3+ often leads to poor kinetics, whereas the rapid diffusion kinetics of hydrated hydrogen ions (H3O+) may offer the solution. However, the presence of considerable Al3+ in the electrolyte hinders the insertion reaction of H3O+. Herein, we report how oxygen‐deficient α‐MoO3 nanosheets unlock selective H3O+ insertion in
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Dehydration‐Induced Cluster Consolidation in a Metal–Organic Framework for Sieving Hexane Isomers Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Zhi-Jie Jiang, Ying Wang, Dong Luo, Rong-Jia Wei, Weigang Lu, Dan Li
Metal–organic frameworks (MOFs) that exhibit dynamic phase‐transition behavior under external stimuli could have great potential in adsorptive separations. Here we report on a zinc‐based microporous MOF (JNU‐80) and its reversible transformation between two crystalline phases: large pore (JNU‐80‐LP) and narrow pore (JNU‐80‐NP). Specifically, JNU‐80‐LP can undergo a dehydration‐induced cluster consolidation
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Type I [4σ + 4π] vs [4σ + 4π ‐ 1] Cycloadditions Accessing Medium‐Sized Carbocycles and Discovery of a Liver X Receptor β‐Selective Ligand Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-22 Cheng Jiang, Lingfei Hu, Shuna Shen, Jianyu Zhang, Xi Wang, Dongxu Ma, Gang Lu, Tao Xu
The transition‐metal‐catalyzed [4 + 4] cycloaddition leading to cyclooctanoids has been centralizing on dimerization between 1,3‐diene type substrates. Here, we extend a [4σ + 4π ‐ 1] and [4σ + 4π] cycloaddition strategy to access the 7/8‐membered fused carbocycles through Rh‐catalyzed coupling between the 4σ‐donor (benzocyclobutenones) and pendant diene (4π) motifs. The two pathways can be controlled
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A Naphthalenetetracarboxdiimide‐Containing Covalent Organic Polymer: Preparation, Single Crystal Structure and Battery Application Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-20 Qiang Dong, Tuoya Naren, Lei Zhang, Weixuan Jiang, Miaomiao xue, Xiang Wang, Libao Chen, Chun-Sing Lee, Qichun Zhang
Inspired by dative boron‐nitrogen (B←N) bonds proven to be the promising dynamic linkage for the construction of crystalline covalent organic polymers/frameworks (COPs/COFs), we employed 1,4‐bis(benzodioxaborole) benzene (BACT) and N,N'‐Di(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxdiimide (DPNTCDI) as the corresponding building blocks to construct a functional COP (named as CityU‐25), which had been
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Catalytic Asymmetric Cascade Dearomatization of Indoles via a Photoinduced Pd‐Catalyzed 1,2‐Bisfunctionalization of Butadienes Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-20 Xiaohang Zhan, Zhiwen Nie, Na Li, Ao Zhou, Haotian Lv, Mingrong Liang, Keqin Wu, Guijuan Cheng, Qin Yin
Photoinduced Pd‐catalyzed bisfunctionalization of butadienes with a readily available organic halide and a nucleophile represents an emerging and attractive method to assemble versatile alkenes bearing various functional groups at the allylic position. However, enantiocontrol and/or diastereocontrol in the C‐C or C‐X bond‐formation step have not been solved due to the open‐shell process. Herein, we
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Temporal‐Focusing Multiphoton Excitation Single‐Molecule Localization Microscopy Using Spontaneously Blinking Fluorophores Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-20 Jian-Zong Lai, Chun-Yu Lin, Shean-Jen Chen, Yu-Min Cheng, Manabu Abe, Tzu-Chau Lin, Fan-Ching Chien
Single‐molecule localization microscopy (SMLM) based on temporal‐focusing multiphoton excitation (TFMPE) and single‐wavelength excitation is used to visualize the three‐dimensional (3D) distribution of spontaneously blinking fluorophore‐labeled subcellular structures in a thick specimen with a nanoscale‐level spatial resolution. To eliminate the photobleaching effect of unlocalized molecules in out‐of‐focus
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Chemical Control of Fluorescence Lifetime towards Multiplexing Imaging Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-20 Junbao Ma, Feng Luo, Chia-Heng Hsiung, Jianan Dai, Zizhu Tan, Songtao Ye, Lina Ding, Baoxing Shen, Xin Zhang
Fluorescence lifetime imaging has been a powerful tool for biomedical research. Recently, fluorescence lifetime‐based multiplexing imaging has expanded imaging channels by using probes that harbor the same spectral channels and distinct excited state lifetime. While it is desirable to control the excited state lifetime of any given fluorescent probes, the rational control of fluorescence lifetimes
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Controlled Biocatalytic Synthesis of a Metal Nanoparticle‐Enzyme Hybrid: Demonstration for Catalytic H2‐driven NADH Recycling Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-20 Lucy B. F. Browne, Tim Sudmeier, Maya A. Landis, Christopher S. Allen, Kylie Alison Vincent
Here we demonstrate the preparation of enzyme‐metal biohybrids of NAD+ reductase with biocatalytically‐synthesised small gold nanoparticles (NPs, <10 nm) and core‐shell gold‐platinum NPs for tandem catalysis. Despite the variety of methods available for NP synthesis, there remains a need for more sustainable strategies which also give precise control over the shape and size of the metal NPs for applications
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Cyclometallated Imides as Templates for the H‐Bond Directed Iridium‐Catalyzed Asymmetric Hydrogenation of N‐Methyl, N‐Alkyl and N‐Aryl Imines Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Yisong Wen, Marc Fernández-Sabaté, Agustí Lledós, Giuseppe Sciortino, James Eills, Irene Marco-Rius, Antoni Riera, Xavier Verdaguer
A combined computational and experimental approach allowed us to develop the most selective catalysts for the direct hydrogenation of N‐methyl and N‐alkyl imines described to date. Iridium catalysts with a cyclometallated cyclic imide group provide selectivity of up to 99% enantiomeric excess. Computational studies show that the selectivity results from the combined effect of H‐bonding of the imide
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Reaction Environment Regulation for Electrocatalytic CO2 Reduction in Acids Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 min Zeng, Wensheng Fang, Yiren Chen, Xinyi Zhang, Yongming Hu, Bao Yu Xia
The electrocatalytic CO2 reduction reaction (CO2RR) is a sustainable route for converting CO2 into value‐added fuels and feedstocks, advancing a carbon‐neutral economy. The electrolyte critically influences CO2 utilization, reaction rate and product selectivity. While typically conducted in neutral/alkaline aqueous electrolytes, the CO2RR faces challenges due to (bi)carbonate formation and its crossover
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Delocalizing Excitation for Highly‐Active Organic Photovoltaic Catalysts Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Zhenzhen Zhang, Chaoying Xu, Qianlu Sun, Yufan Zhu, Wenlong Yan, Guilong Cai, Yawen Li, Wenqin Si, Xinhui Lu, Weigao Xu, Ye Yang, Yuze Lin
Localized excitation in traditional organic photocatalysts typically prevents the generation and extraction of photo‐induced free charge carriers, limiting their activity enhancement under illumination. Here, we enhance delocalized photoexcitation of small molecular photovoltaic catalysts by weakening their electron‐phonon coupling via rational fluoro‐substitution. The optimized 2FBP‐4F catalyst we
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Reversal of the Regioselectivity of Iron‐Promoted Hydrogenation and Hydrohalogenation of gem‐Difluoroalkenes Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Yu-Yang Zhang, Yuchen Zhang, Xiao-Song Xue, Feng-Ling Qing
The reaction regioselectivity of gem‐difluoroalkenes is dependent on the intrinsic polarity. Thus, the reversal of the regiose‐lectivity of the addition reaction of gem‐difluoroalkenes remains a formidable challenge. Herein, we described an unprecedented reversal of regioselectivity of hydrogen atom transfer (HAT) to gem‐difluoroalkenes triggered by Fe–H species for the formation of difluoroalkyl radicals
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Cyclodextrin ‘Chaperones’ Enable Quasi‐Ideal Supramolecular Network Formation and Enhanced Photodimerization of Hydrophobic, Red‐shifted Photoswitches in Water Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Daniel Hoenders, Simon Ludwanowski, Christopher Barner-Kowollik, Andreas Walther
Precision‐engineered light‐triggered hydrogels are important for a diversity of applications. However, fields such as biomaterials require wavelength outside the harsh UV regime to prevent photodamage, typically requiring chromophores with extended p‐conjugation that suffer from poor water solubility. Herein, we demonstrate how cyclodextrins can be used as auxiliary agents to not only solubilize such
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One‐Component Cationic Lipids for Systemic mRNA Delivery to Splenic T Cells Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Xinyue Zhang, Kexin Su, Shiqi Wu, Lixin Lin, Shun He, Xinxin Yan, Lu Shi, Shuai Liu
Unlocking the full potential of mRNA immunotherapy necessitates targeted delivery to specific cell subsets in the spleen. Four‐component lipid nanoparticles (LNPs) utilized in numerous clinical trials are primarily limited in hepatocyte and muscular targeting, highlighting the imperative demand for targeted and simplified non‐liver mRNA delivery systems. Herein, we report the rational design of one‐component
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M‐N3 Configuration on Boron Nitride Boosts Singlet Oxygen Generation via Peroxymonosulfate Activation for Selective Oxidation Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Jianzheng Zhen, Jiahao Sun, Xiangwei Xu, Zenglong Wu, Wenkai Song, Yunzhan Ying, Shikun Liang, Lingshan Miao, Jiazhen Cao, Weiyang Lv, Changsheng Song, Yuyuan Yao, Mingyang Xing
Singlet oxygen (1O2) is an essential reactive species responsible for selective oxidation of organic matter, especially in Fenton‐like processes. However, due to the great limitations in synthesizing catalysts with well‐defined active sites, the controllable production and practical application of 1O2 remain challenging. Herein, guided by theoretical simulations, a series of boron nitride‐based single‐atom
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A MOF@Metal Oxide Heterostructure Induced by Post‐Synthetic Gamma‐Ray Irradiation for Catalytic Reduction Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Mingxing Zhang, Junchang Chen, Xiaofang Zhao, Xuanzhi Mao, Chunyang Li, Juan Diwu, Guozhong Wu, Zhifang Chai, Shuao Wang
Metal‐organic framework (MOF) based heterostructures, which exhibit enhanced or unexpected functionality and properties due to synergistic effects, are typically synthesized using post‐synthetic strategies. However, several reported post‐synthetic strategies remain unsatisfactory, considering issues such as damage to the crystallinity of MOFs, presence of impure phases, and high time and energy consumption
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NIR‐II Fluorescence Sensor Based on Steric Hindrance Regulated Molecular Packing for In Vivo Epilepsy Visualization Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Mengyao Zhao, Weiping Lai, Benhao Li, Tianwen Bai, Chunyan Liu, Yanfei Lin, Shixuan An, Longhua Guo, Lei Li, Jianbo Wang, Fan Zhang
Fluorescence sensing is crucial to study biological processes and diagnose diseases, especially in the second near‐infrared (NIR‐II) window with reduces background signals. However, it's still a great challenge to construct "off‐on" sensors when the sensing wavelength extends into the second near‐infrared (NIR‐II) region to obtain higher imaging contrast, mainly due to the difficult synthesis of spectral
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Machine Learning Molecular Dynamics Shows Anomalous Entropic Effect on Catalysis via Surface Pre‐melting of Nanoclusters Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Fu-Qiang Gong, Yun-Pei Liu, Ye Wang, Weinan E, Zhong-Qun Tian, Jun Cheng
Due to the superior catalytic activity and efficient utilization of noble metals, nanocatalysts are extensively used in the modern industrial production of chemicals. The surface structures of these materials are significantly influenced by reactive adsorbates, leading to dynamic behavior under experimental conditions. The dynamic nature poses significant challenges in studying the structure‐activity
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The 18F‐Difluoromethyl Group: Challenges, Impact and Outlook Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Joseph Ford, Sebastiano Ortalli, Veronique Gouverneur
The difluoromethyl functionality has proven useful in drug discovery, as it can modulate the properties of bioactive molecules. For PET imaging, this structural motif has been largely underexploited in (pre)clinical radiotracers due to a lack of user‐friendly radiosynthetic routes. This Minireview provides an overview of the challenges facing radiochemists and summarises the efforts made to date to
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Linker Mediated Electronic‐State Manipulation of Conjugated Organic Polymers Enabling Highly Efficient Oxygen Reduction Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Rui Ma, Chenglong Tang, Yonglin Wang, Xiaoxue Xu, Mingjie Wu, Xun Cui, Yingkui Yang
Conjugated polymers with tailorable composition and microarchitecture are propitious for modulating catalytic properties and deciphering inherent structure‐performance relationships. Herein, we report a facile linker engineering strategy to manipulate the electronic states of metallophthalocyanine conjugated polymers and uncover the vital role of organic linkers in facilitating electrocatalytic oxygen
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An All‐rounder for NIR‐II Phototheranostics: Well‐Tailored 1064 nm Excitable Molecule for Photothermal Combating Orthotopic Breast Cancer Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Dingyuan Yan, Zhijun Zhang, Jianyu Zhang, Xue Li, Qian Wu, Yixiong Gui, Jun Zhu, Miaomiao Kang, Xiaohui Chen, Ben Zhong Tang, Dong Wang
The second near‐infrared (NIR‐II, 1000–1700 nm) light‐activated organic photothermal agent that synchronously enables satisfying NIR‐II fluorescence imaging is highly warranted yet rather challenging on the basis of the overwhelming nonradiative decay. Herein, such an agent, namely TPABT‐TD, was tactfully designed and constructed via employing benzo[c]thiophene moiety as bulky electron donor/π‐bridge
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Hydrogen‐Bond‐Mediated Formation of C‐N or C=N Bond during Photocatalytic Reductive Coupling Reaction over CdS Nanosheets Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-19 Jie He, Bo Han, Chensheng Xian, Zhao Hu, Tingfeng Fang, Zehui Zhang
Reductive amination of carbonyl compounds and nitro compounds represents a straightforward way to attain imines or secondary amines, but it is difficult to control the product selectivity. Herein, we report the selective formation of C−N or C=N bond readily manipulated through a solvent‐induced hydrogen bond bridge, facilitating the swift photocatalytic reductive coupling process. The reductive‐coupling