Angewandte Chemie International Edition最新文献_第7页

Potassium Tetraiodatoiodate(III) Iodate(V): A Nonlinear Optical Crystal with Exceptional Second-Harmonic Generation and Full-Wavelength Phase Matching

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202504673

Min-Quan Lin, Chun-Li Hu, Meng-Fan Duan, Bing-Xuan Li, Jiang-Gao Mao, Bing-Ping Yang

{"title":"Potassium Tetraiodatoiodate(III) Iodate(V): A Nonlinear Optical Crystal with Exceptional Second-Harmonic Generation and Full-Wavelength Phase Matching","authors":"Min-Quan Lin, Chun-Li Hu, Meng-Fan Duan, Bing-Xuan Li, Jiang-Gao Mao, Bing-Ping Yang","doi":"10.1002/anie.202504673","DOIUrl":"https://doi.org/10.1002/anie.202504673","url":null,"abstract":"The development of nonlinear optical materials with large nonlinear optical susceptibilities, wide transmission ranges, and comprehensive full-wavelength phase matching capabilities remains a significant challenge. In this study, we synthesized a novel potassium tetraiodatoiodate(III) iodate(V) via an in situ reduction and complexation reaction. The resulting compound, K2[IIII(IVO3)4]IVO3, exhibits exceptional second harmonic generation responses (21.6KH2PO4 at 1064 nm, 1.0KTiOPO4 at 2050 nm), a wide transparency range from the visible to the mid-infrared wavelengths (0.37–6.05 μm and 7.03–13.40 μm), and a high birefringence (0.358 at 543 nm) to achieve full-wavelength phase matching. These properties are primarily ascribed to the synergistic substantial hyperpolarizability and polarizability anisotropy exhibited by the [IIII(IVO3)4]− complex ions, which comprise square-planar coordinated trivalent iodine and optimally arranged iodate ligands. This study demonstrates the pivotal role of nonmetallic cation centered coordination entities in influencing linear and nonlinear optical properties, a discovery that has significant implications for the development of innovative inorganic functional materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"76 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737286","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}

引用次数: 0

Concise Total Syntheses of Leuconoxine-Type Alkaloids Enabled by Palladium/Norbornene-Catalyzed Pyrrole Difunctionalization

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202502736

Xin Liu, Yun Zhou, Yu Meng, Qi Zhu, Renhe Li, Guangbin Dong

引用次数: 0

Oxygen Atom Migration Dominates Anomalous Reversible Oxidation of Ru Nanosheets

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202502927

Xiong Xiao, Yongli Shen, Wei Xi, Lin Gu, Xiaogang Li, Baojuan Xi, Shenglin Xiong, Changhua An

{"title":"Oxygen Atom Migration Dominates Anomalous Reversible Oxidation of Ru Nanosheets","authors":"Xiong Xiao, Yongli Shen, Wei Xi, Lin Gu, Xiaogang Li, Baojuan Xi, Shenglin Xiong, Changhua An","doi":"10.1002/anie.202502927","DOIUrl":"https://doi.org/10.1002/anie.202502927","url":null,"abstract":"Oxidation is a ubiquitous reaction in nature. For most metals (especially metal nanoparticles), they will be completely oxidized under suitable conditions, except ruthenium (Ru). In this work, in‐situ transmission electron microscopy (in‐situ TEM) and ex‐situ spectroscopy were employed to investigate the oxidation process of Ru nanosheets. Ex‐situ spectroscopic analysis demonstrates the incomplete oxidation of Ru nanosheets to RuO₂, while the in‐situ TEM observations uncover an anomalous reverse phase transformation from the oxidized to metallic phase during oxidation. Combined with theoretical calculations, the oxygen atom migration dominates the reversible oxidation process, strikingly distinct from the unidirectional oxidation pathways in conventional metallic systems. The as‐generated abundant Ru‐RuO2 heterointerfaces formed through reversible oxidation provide a wealth of active sites for electrochemical alkaline hydrogen evolution reaction (HER). Herein, the study not only lays a foundation for the understanding complex dynamic oxidation processes, but also offers new insights into for the design of nanocatalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"31 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736720","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}

引用次数: 0

Annulated Radical Cations with a C4E2‐Core (E = P, As, Sb): Stable Pnictogen Analogs of Elusive Aryl Radical Anions of Birch Reduction Reactions

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202505142

Henric Steffenfauseweh, Yury V. Vishnevskiy, Beate Neumann, Hans-Georg Stammler Stammler, Demi Snabilié, Bas de de Bruin, Rajendra Ghadwal

{"title":"Annulated Radical Cations with a C4E2‐Core (E = P, As, Sb): Stable Pnictogen Analogs of Elusive Aryl Radical Anions of Birch Reduction Reactions","authors":"Henric Steffenfauseweh, Yury V. Vishnevskiy, Beate Neumann, Hans-Georg Stammler Stammler, Demi Snabilié, Bas de de Bruin, Rajendra Ghadwal","doi":"10.1002/anie.202505142","DOIUrl":"https://doi.org/10.1002/anie.202505142","url":null,"abstract":"The benzene radical anion (C6H6)●–, possessing a 7π‐electron count, is a crucial intermediate in the Birch reduction and has been extensively studied both experimentally and theoretically. Herein, we report the tricyclic pnictogen radical cations [(ADC)E]2[B], [2‐E][B] (ADC = PhC{N(Dipp)C}2; Dipp = 2,6‐iPr2C6H3; E = P, As, Sb; [B] = [B1] = B(C6F5)4 or [B2] = {3,5‐(CF3)2C6H3}) featuring a central 7π‐electron planar C4E2 ring embedded between two 1,3‐imidazole‐based anionic dicarbene (ADC) frameworks, as crystalline solids. [2‐E][B] are prepared by one‐electron (1e) oxidations of the corresponding base‐stabilized cyclic pnictinidene compounds [(ADC)E]2 (1‐E). Calculated spin densities (for E = P 76%, As 80%, Sb 88%) and EPR measurements suggest that [2‐E]●+ are pnictogen‐centered radicals and stabilized by the delocalization of the unpaired electron over the C4E2 ring. The EPR spectra of [2‐E][B] exhibit characteristic signals for S = ½ systems with clear hyperfine coupling constants for the two similar P, As or Sb nuclei. Further 1e‐oxidations of [2‐E][B] result in the dicationic 6π‐electron C4E2‐species [(ADC)E]2[B]2 [3‐E][B]2, which readily undergo comproportionations with 1‐E to afford [2‐E][B]. The radical reactivity of [2‐E][B2] is shown with 2,2,6,6‐tetramethylpiperidinyloxyl (TEMPO) and diphenyl diselenide (PhSeSePh) in yielding compounds [(ADC)2E{E(TEMPO)}][B2] (4‐E) (E = P, Sb) and [(ADC)2P{P(SePh)}][B2] (5‐P), respectively.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"96 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736742","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}

引用次数: 0

Data-Driven Review on Aerogels and Polymeric Aerogels

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202504250

Satoru Takeshita, Shinya Mine, Takumi Ono

引用次数: 0

Controlled Growth of Oligophenylene‐Structures on Graphene for Facile Secondary functionalization.

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202504482

Christian Eberhard Halbig, Markus R. Heinrich, Felix Fels, Shenquan Wei, Siegfried Eigler, Robert Schusterbauer, Ievgen Donskyi

{"title":"Controlled Growth of Oligophenylene‐Structures on Graphene for Facile Secondary functionalization.","authors":"Christian Eberhard Halbig, Markus R. Heinrich, Felix Fels, Shenquan Wei, Siegfried Eigler, Robert Schusterbauer, Ievgen Donskyi","doi":"10.1002/anie.202504482","DOIUrl":"https://doi.org/10.1002/anie.202504482","url":null,"abstract":"Functionalization of graphene derivatives is a common approach to tune material properties for use in various applications. Due to the low reactivity of the unsaturated carbon lattice of graphene, not only are few chemical approaches suitable for successful functionalization, such as those involving highly reactive in situ formed radical species or nitrene and carbene compounds, but also the degree of functionalization is usually limited, modifying only a few percent of the carbon atoms. Typically, uncontrolled side reactions such as homocoupling and oligomerization of newly introduced functional groups can occur instead of direct coupling to the carbon lattice. We want to turn this unwanted side reaction into an advantage and use intentionally formed covalent dendrimeric oligophenylene structures for secondary functionalization. We show that these oligomeric structures can be grown to specific thicknesses and used for further functionalization with bromomethyl groups at high density on the surface. This functionalization opens further avenues for subsequent nucleophilic substitution, as exemplified by the introduction of versatile azide, nitrile, and phosphonate groups. The results presented here are not only applicable to large oligophenylene structures, but also demonstrate that, in principle, single aryl moieties on graphene of any size and density can be successfully functionalized.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"166 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736748","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}

引用次数: 0

Pressure‐Induced Emission Luminogens Enable Optical Logic Gates toward Lighting, Scintillators and Anti‐counterfeiting

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202504913

Wenya Zhao, Guanjun Xiao, Shi Qiu, Yuchen Shang, Yue Qin, Jiayi Yang, Jingtian Wang, Jiajia Ning, Yanjun Fang, Qingfeng Dong, Zhaodong Liu, Shunxin Li, Junfeng Gao, Bo Zou

{"title":"Pressure‐Induced Emission Luminogens Enable Optical Logic Gates toward Lighting, Scintillators and Anti‐counterfeiting","authors":"Wenya Zhao, Guanjun Xiao, Shi Qiu, Yuchen Shang, Yue Qin, Jiayi Yang, Jingtian Wang, Jiajia Ning, Yanjun Fang, Qingfeng Dong, Zhaodong Liu, Shunxin Li, Junfeng Gao, Bo Zou","doi":"10.1002/anie.202504913","DOIUrl":"https://doi.org/10.1002/anie.202504913","url":null,"abstract":"The pressure‐induced emission luminogens (PIEgens) opened the door to highly emissive materials. However, the high‐pressure phase with excellent optoelectrical properties is difficult to be stabilized at ambient conditions, seriously limiting the practical applications. Here, we firstly lighted up non‐emissive zero‐dimensional (0D) metal halide (C25H22P)2SnCl6 via pressure engineering, ultimately yielding the bright emission. Note that the quenched (C25H22P)2SnCl6 after pressure treatment of 20.0 GPa exhibited the very bright blue‐white emission. This irreversible photoluminescence (PL) transition was associated with the irreversible amorphization by increasing the potential barrier of phase transition through the steric hindrance effect. The increased distortion of inorganic octahedra and the enhanced hydrogen bond interaction within the amorphous (C25H22P)2SnCl6 after pressure treatment were responsible for the bright emission. Thus pressure‐triggered PL turn‐on behavior can serve as a robust optical switchable logic gate from the initially dark state “0” to the bright state “1”. Furthermore, the pressure‐treated (C25H22P)2SnCl6 exhibited an unexpected excitation‐dependent emission. The unique characteristic of “PIE” with different colors can be decoded the Morse code encrypted with the pressure‐treated (C25H22P)2SnCl6 and different excitations. The quenched (C25H22P)2SnCl6‐based phosphor‐converted light‐emitting diodes (pc‐LEDs), X‐ray dose rate detection and centimeter‐level patterns highlighted great potentials in lighting, display, scintillators, and anti‐counterfeiting.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"90 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736744","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}

引用次数: 0

Regioselective Nickel‐catalyzed Hydroarylation of gem‐Difluoroalkenes for the Synthesis of the ArCF2‐ Moiety

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202424714

Xiangyu Chen, Ruitong Zhang, Yaxing Wu, Fei Wang, Chao Chen

引用次数: 0

Peripheral Engineering of Multiple‐Resonance Framework Targeting Efficient Organic Lasers

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202504652

Chihaya Adachi, Tuul Tsagaantsooj, Xun Tang, Tao Zhang, Yi-Ting Lee, Rajat Walia, Xian-kai Chen

{"title":"Peripheral Engineering of Multiple‐Resonance Framework Targeting Efficient Organic Lasers","authors":"Chihaya Adachi, Tuul Tsagaantsooj, Xun Tang, Tao Zhang, Yi-Ting Lee, Rajat Walia, Xian-kai Chen","doi":"10.1002/anie.202504652","DOIUrl":"https://doi.org/10.1002/anie.202504652","url":null,"abstract":"Multiple‐resonance thermally activated delayed fluorescent (MR‐TADF) emitters have emerged as promising candidates for organic laser applications due to the potential for simultaneously achieving large oscillator strength and triplet utilization. In this study, we investigate the impact of peripheral tert‐butyl (t‐Bu)‐ and phenyl (Ph)‐substituents on the typical 9‐(phenylcarbazol‐3‐yl)‐9H‐carbazole‐3‐carbonitrile (CzBN) MR framework. While these modifications preserve the frontier molecular orbital distribution with large oscillator strengths, they significantly influence excited‐state dynamics and molecular aggregation at even low doping concentrations. Introducing Ph substituents extends the π‐conjugation extension of CzBN, promoting closer molecular packing, detrimental molecular aggregation, and significantly broadening the excited‐state absorption (ESA) band, which negatively impacts lasing performance. In contrast, CzBN‐tBu, incorporating t‐Bu groups as non‐conjugated substituents, demonstrated reduced molecular aggregation and a distinct separation between the ESA band and stimulated emission region. Consequently, the optimal distributed feedback lasing performance is achieved by CzBN‐tBu across various doping concentrations, resulting in the lowest lasing threshold of 3.4 µJ cm−2. These findings underscore the impact of inherent aggregation at low doping ratio on lasing activities, highlighting the crucial role of rational peripheral engineering in modulating molecular interactions and excited‐state dynamics, offering design strategies for developing MR lasing molecules.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"42 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736747","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}

引用次数: 0

Modulating the Chromophores of Metal-Covalent Organic Frameworks for Boosting Low-Concentration CO2 Photoreduction

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-31 DOI: 10.1002/anie.202505292

Chong-Jiu Lu, Ji-Hong Zhang, Jian-Hua Mei, Yun-Nan Gong, Tong-Bu Lu, Di-Chang Zhong

{"title":"Modulating the Chromophores of Metal-Covalent Organic Frameworks for Boosting Low-Concentration CO2 Photoreduction","authors":"Chong-Jiu Lu, Ji-Hong Zhang, Jian-Hua Mei, Yun-Nan Gong, Tong-Bu Lu, Di-Chang Zhong","doi":"10.1002/anie.202505292","DOIUrl":"https://doi.org/10.1002/anie.202505292","url":null,"abstract":"The development of efficient photocatalysts to convert low-concentration CO2 into the value-added chemicals and fuels is particularly interesting yet remains highly challenging. Herein, we designed and synthesized three metal-covalent organic frameworks (MCOFs) through the Schiff-base condensation reactions between trinuclear copper complex and different BDP-based chromophores (BDP = 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) for visible-light-driven reduction of low-concentration CO2 (15%) to HCOO-. As a result, MCOF-ANT containing anthracene (ANT) group achieves the highest HCOO- production rate of 1658 μmol g-1 h-1 (HCOO- selectivity, ~100%) in the absence of any additional noble-metal photosensitizers under a laboratory light source, which is 7.2 and 2.1 times higher than those of MCOF-Ph and MCOF-Nap with phenyl (Ph) and naphthalene (Nap) groups, respectively. Furthermore, MCOF-ANT also exhibits an excellent photocatalytic activity for the reduction of low-concentration CO2 (15%) to HCOO- under natural sunlight, with a HCOO- production rate of 1239 μmol g-1 h-1 (HCOO- selectivity, ~100%). Experiments and theoretical calculations reveal that the presence of ANT in MCOF-ANT is favorable to the visible-light harvesting and charge separation, as well as the formation of *OCO intermediate, which clearly accounts for its superior catalytic activity.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737284","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}

引用次数: 0