Molecular Engineering for Modulating Photocatalytic Hydrogen Evolution of Fully Conjugated 3D Covalent Organic Frameworks
Angew Chem Int Ed Engl. 2024 Apr 15:e202404726. doi: 10.1002/anie.202404726. Online ahead of print.ABSTRACTCovalent organic frameworks (COFs) have recently shown great potential for photocatalytic hydrogen production. Currently almost all reports are focused on two-dimensional (2D) COFs, while the 3D counterparts are rarely explored due to their non-conjugated frameworks derived from the sp3 carbon based tetrahedral building blocks. Here, we rationally designed and synthesized a series of fully conjugated 3D COFs by using the saddle-shaped cyclooctatetrathiophene derivative as the building block. Through molecular engineer...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Yaqin Wang Zelong Qiao Han Li Rui Zhang Zhonghua Xiang Dapeng Cao Shitao Wang Source Type: research
Ethylenedioxythiophene-based Small Molecular Donor with Multiple Conformation Locks for Organic Solar Cells with Efficiency of 19.3
In this study, a novel class of conjugated small molecules has been introduced as the third component, demonstrating exceptional photovoltaic performance in T-OSCs. This innovative molecule comprises ethylenedioxythiophene (EDOT) bridge and 3-ethylrhodanine as the end group, with the EDOT unit facilitating the creation of multiple conformation locks. Consequently, the EDOT-based molecule exhibits two-dimensional charge transport, distinguishing it from the thiophene-bridged small molecule, which displays fewer conformation locks and provides one-dimensional charge transport. Furthermore, the robust electron-donating nature...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Qian Xie Xiangmeng Deng Chaowei Zhao Jie Fang Dongdong Xia Yuefeng Zhang Feng Ding Jiali Wang Mengdi Li Zhou Zhang Chengyi Xiao Xunfan Liao Lang Jiang Bin Huang Runying Dai Weiwei Li Source Type: research
Electrochemical Asymmetric Radical Functionalization of Aldehydes Enabled by a Redox Shuttle
Angew Chem Int Ed Engl. 2024 Apr 16:e202401361. doi: 10.1002/anie.202401361. Online ahead of print.ABSTRACTAminocatalysis is a well-established tool that enables the production of enantioenriched compounds under mild conditions. Its versatility is underscored by its seamless integration with various synthetic approaches. While the combination of aminocatalysis with metal catalysis, photochemistry, and stoichiometric oxidants has been extensively explored, its synergy with electrochemical activation remains largely unexplored. Herein, we present the successful merger of electrochemistry and aminocatalysis to perform SOMO-ty...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Daniele Mazzarella Chun Qi Michael Vanzella Andrea Sartorel Giorgio Pelosi Luca Dell'Amico Source Type: research
N-(sulfonio)sulfilimine reagents: Non-oxidizing Sources of Electrophilic Nitrogen Atom for Skeletal Editing
Angew Chem Int Ed Engl. 2024 Apr 16:e202403826. doi: 10.1002/anie.202403826. Online ahead of print.ABSTRACTThe one-pot synthesis of λ4-dibenzothiophen-5-imino-N-dibenzothiophenium triflate (1) in multigram scale is reported. This compound reacts with Rh2(esp)2 (esp = α,α,α',α'-tetramethyl-1,3-benzenedipropionic acid) generating a Rh-coordinated sulfonitrene species, which is able to transfer the electrophilic nitrene moiety to olefins. When indenes are used as substrates, isoquinolines are obtained in good yields. We assumed that after formation of the corresponding N-sulfonio aziridine, a ring expansion occurs via se...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Tobias Heilmann Juan M Lopez-Soria Johannes Ulbrich Johannes Kircher Zhen Li Brigitte Worbs Christopher Golz Ricardo A Mata Manuel Alcarazo Source Type: research
Engineering of Halide Methyltransferase BxHMT through Dynamic Cross-correlation Network Analysis
Angew Chem Int Ed Engl. 2024 Apr 16:e202401235. doi: 10.1002/anie.202401235. Online ahead of print.ABSTRACTHalide methyltransferases (HMTs) provide an effective way to regenerate S-adenosyl methionine (SAM) from S-adenosyl homocysteine and reactive electrophiles such as methyl iodide (MeI) or methyl toluene sulfonate (MeOTs). Compared with MeI, the cost-effective unnatural substrate MeOTs can be accessible directly from cheap and abundant alcohols, but shows only limited reactivity in SAM production. Herein, we developed a dynamic cross-correlation network analysis (DCCNA) strategy for quickly identifying hot spots influen...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Chun-Yu Gao Gui-Ying Yang Xu-Wei Ding Jian-He Xu Xiaolin Cheng Gao-Wei Zheng Q I Chen Source Type: research
Two-Dimensional Conjugated Metal-Organic Frameworks with a Ring-in-Ring Topology and High Electrical Conductance
In this study, we have employed a novel highly branched D3h symmetrical planar conjugated ligand, dodechydroxylhexabenzotrinaphthylene (DHHBTN) to fabricate a series of 2D conductive MOFs, named M-DHHBTN (M = Co, Ni, and Cu). This new family of MOFs offers two distinct types of pores, elevating the structural complexity of 2D conductive MOFs to a more advanced level. The intricate tessellation patterns of the M-DHHBTN are elucidated through comprehensive analyses involving powder X-ray diffraction, theoretical simulations, and high-resolution transmission electron microscope. Optical-pump terahertz-probe spectroscopic meas...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Mingyu Yang Yi Zhang Renlong Zhu Junjun Tan Jinxin Liu Wei Zhang Meng Zhou Zheng Meng Source Type: research
Unveiling Crucial Chemical Processing Parameters Influencing the Performance of Solution-processed Inorganic Thermoelectric Materials
Angew Chem Int Ed Engl. 2024 Apr 16:e202402628. doi: 10.1002/anie.202402628. Online ahead of print.ABSTRACTProduction of thermoelectric materials from solution-processed particles involves the synthesis of particles, their purification and densification into pelletized material. Chemical changes that occur during each one of these steps render them performance determining. Particularly the purification steps, bypassed in conventional solid-state synthesis, are the cause for large discrepancies among similar solution-processed materials. In present work, the investigation focuses on a water-based surfactant free solution sy...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Christine Fiedler Mariano Calcabrini Yu Liu Maria Ib áñez Source Type: research
Anion-Coordination Foldamer-Based Polymer Network: from Molecular Spring to Elastomer
Angew Chem Int Ed Engl. 2024 Apr 16:e202400989. doi: 10.1002/anie.202400989. Online ahead of print.ABSTRACTFoldamer is a scaled-down version of coil spring, which can absorb and release energy by conformational change. Here, polymer networks with high-density of molecular springs were developed by employing anion-coordination-based foldamers as the monomer. The coiling of the foldamer is controlled by oligourea ligands coordinating to chloride ions; subsequently, the folding and unfolding of foldamer conformations endow the polymer network with excellent energy dissipation and toughness. The mechanical performance of the c...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Jiangping Qin Yongming Wang Tian Wang Na Wang Wenhua Xu Lin Cheng Wei Yu Xuzhou Yan Lingyan Gao Bo Zheng Biao Wu Source Type: research
Ternary Rotational Polyanion Coupling Enables Fast Li Ion Dynamics in Tetrafluoroborate Ion Doped Antiperovskite Li2OHCl Solid Electrolyte
Angew Chem Int Ed Engl. 2024 Apr 16:e202400144. doi: 10.1002/anie.202400144. Online ahead of print.ABSTRACTLi-rich antiperovskite (LiRAP) hydroxyhalides are emerging as attractive solid electrolyte (SEs) for all-solid-state Li metal batteries (ASSLMBs) due to their low melting point, low cost, and ease of scaling-up. The incorporation of rotational polyanions can reduce the activation energy and thus improve the Li ion conductivity of SEs. Herein, we propose a ternary rotational polyanion coupling strategy to fasten the Li ion conduction in tetrafluoroborate (BF4-) ion doped LiRAP Li2OHCl. Assisted by first-principles calc...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Juncao Bian Sifan Ling Bei Deng Haibin Lin Ruo Zhao Long Kong Huimin Yuan Jinlong Zhu Songbai Han Liping Wang Ruiqin Zhang Yusheng Zhao Zhouguang Lu Source Type: research
Non-Fluorinated Ethers to Mitigate Electrode Surface Reactivity in High-Voltage NCM811-Li Batteries
Angew Chem Int Ed Engl. 2024 Apr 16:e202404109. doi: 10.1002/anie.202404109. Online ahead of print.ABSTRACTLithium (Li) metal batteries (LMBs) with nickel (Ni)-rich layered oxide cathodes exhibit twice the energy density of conventional Li-ion batteries. However, their lifespan is limited by severe side reactions caused by high electrode reactivity. Fluorinated solvent-based electrolytes can address this challenge, but they pose environmental and biological hazards. This work reports on the molecular engineering of fluorine (F)-free ethers to mitigate electrode surface reactivity in high-voltage Ni-rich LMBs. By merely ext...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Zhijie Wang Xiangli Che Danni Wang Yanyan Wang Xiaomei He Ye Zhu Biao Zhang Source Type: research
Expedient Access to 18F-Fluoroheteroarenes via Deaminative Radiofluorination of Aniline-Derived Pyridinium Salts
Angew Chem Int Ed Engl. 2024 Apr 16:e202404945. doi: 10.1002/anie.202404945. Online ahead of print.ABSTRACTHerein, we disclose that pyridinium salts derived from abundant (hetero)anilines represent a novel precursor class for nucleophilic aromatic substitution reactions with [18F]fluoride. The value of this new 18F-fluorodeamination is demonstrated with the synthesis of over 30 structurally diverse and complex heteroaryl 18F-fluorides, several derived from scaffolds that were yet to be labelled with fluorine-18. The protocol tolerates heteroarenes and functionalities commonly found in drug discovery libraries, and is amena...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Joseph Ford Sebastiano Ortalli Zijun Chen Jeroen Sap Matthew Tredwell Veronique Gouverneur Source Type: research
Selective Arylation of RNA 2'-OH Groups via SNAr Reaction with Trialkylammonium Heterocycles
Angew Chem Int Ed Engl. 2024 Apr 16:e202403496. doi: 10.1002/anie.202403496. Online ahead of print.ABSTRACTSmall-molecule reactions at the 2'-OH groups of RNA enable useful applications for transcriptome technology and biology. To date, all reactions have involved carbonyl acylation and mechanistically related sulfonylation, limiting the types of modifications and properties that can be achieved. Here we report that electron-deficient heteroaryl species selectively react with 2'-OH groups of RNA in water via SNAr chemistry. In particular, trialkyl-ammonium (TAA)-activated aromatic heterocycles, prepared in one step from ar...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Sayantan Chatterjee Lu Xiao Wenrui Zhong Sheng Feng Eric T Kool Source Type: research
Mitigating Sodium Ordering for Enhanced Solid Solution Behavior in Layered NaNiO2 Cathodes
We present here a systematic investigation of the impact of substituting 5% divalent (Mg2+) or trivalent (Al3+ or Co3+) ions for Ni3+ to alleviate Na+-ion ordering and perturb the Jahn-Teller effect to enhance structural stability. We gauge a fundamental understanding of the Mg-O and Na-O or Mg-O-Na bonding interactions, noting that the ionicity of the Mg-O bond deshields the electronic cloud of oxygen from Na+ ions. Furthermore, calculations of the Van Vleck distortion modes reveal a relaxation of NiO6 octahedra from Jahn-Teller distortion and a reduced electron density at the interlayer with Mg2+ substitution. Long-range...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Krishnakanth Sada Steven Kmiec Arumugam Manthiram Source Type: research
Ternary Complex-Templated Dynamic Combinatorial Chemistry for the Selection and Identification of Homo-PROTACs
Angew Chem Int Ed Engl. 2024 Apr 16:e202319456. doi: 10.1002/anie.202319456. Online ahead of print.ABSTRACTDynamic combinatorial chemistry (DCC) leverages a reversible reaction to generate compound libraries from constituting building blocks under thermodynamic control. The position of this equilibrium can be biased by addition of a target macromolecule towards enrichment of bound ligands. While DCC has been applied to select ligands for a single target protein, its application to identifying chimeric molecules inducing proximity between two proteins is unprecedented. In this proof-of-concept study, we develop a DCC approa...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Claudia J Diehl Alessandra Salerno Alessio Ciulli Source Type: research
A Zeolitic Octahedral Metal Oxide with Ultrahigh Porosity for High-temperature and High-humidity Alkyne/Alkene Separation
Angew Chem Int Ed Engl. 2024 Apr 16:e202406374. doi: 10.1002/anie.202406374. Online ahead of print.ABSTRACTZeolitic octahedral metal oxide is a newly synthesized all-inorganic zeolitic material and has been used for adsorption, separation, and catalysis. Herein, a new zeolitic octahedral metal oxide was synthesized and characterized. The porous framework was established through the assembly of [P2Mo13O50] clusters with PO4 linkers. Guest molecules occupied the framework, which could be removed through heat treatment, thereby opening the micropores. The pore characteristics were controlled by the cations within the micropor...
Source: Angewandte Chemie - April 16, 2024 Category: Chemistry Authors: Baokai Ma Panpan Hu Liangcheng Zou Qianqian Zhu Lifeng Zhang Satoshi Ishikawa Wataru Ueda Yanshuo Li Zhenxin Zhang Source Type: research
