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51.
Dr. Wenqing Wang Xiao-Hui Ma Min Liu Shuxuan Tang Xuguang Ding Yue Zhao Prof. Yuan-Zhi Tan Prof. Miklos Kertesz Prof. Xinping Wang 《Angewandte Chemie (International ed. in English)》2023,62(8):e202217788
We report on the largest open-shell graphenic bilayer and also the first example of triply negatively charged radical π-dimer. Upon three-electron reduction, bilayer nanographene fragment molecule (C96H24Ar6)2 (Ar=2,6-dimethylphenyl) ( 1 2) was transformed to a triply negatively charged species 1 23.−, which has been characterized by single-crystal X-ray diffraction, electron paramagnetic resonance (EPR) spectroscopy and magnetic properties on a superconducting quantum interference device (SQUID). 1 23.− features a 96-center-3-electron (96c/3e) pancake bond with a doublet ground state, which can be thermally excited to a quartet state. It consists of 34 π-fused rings with 96 conjugated sp2 carbon atoms. Spin frustration is observed with the frustration parameter f>31.8 at low temperatures in 1 23.−, which indicates graphene upon reduction doping may behave as a quantum spin liquid. 相似文献
52.
Dr. Peng Zhang Qian-Cheng Luo Dr. Zhenhua Zhu Wanrong He Nan Song Junting Lv Xuning Wang Prof. Quan-Guo Zhai Prof. Yan-Zhen Zheng Prof. Jinkui Tang 《Angewandte Chemie (International ed. in English)》2023,62(12):e202218540
The syntheses and magnetic properties of organometallic heterometallic compounds [K(THF)6]{CoI[(μ3-HAN)RE2Cp*4]2} ( 1-RE ) and [K(Crypt)]2{CoI[(μ3-HAN)RE2Cp*4]2} ( 2-RE ) containing hexaazatrinaphthylene radicals (HAN⋅3−) and four rare earth (RE) ions are reported. 1-RE shows isolable species with ligand-based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2-RE via one-electron chemical reduction. Strong electronic communication in mixed-valency supports stronger overall ferromagnetic behaviors in 2-RE than 1-RE containing Gd and Dy ions. Ac magnetic susceptibility data reveal 1-Dy and 2-Dy both exhibit slow magnetic relaxation. Importantly, larger coercive field was observed in the hysteresis of 2-Dy at 2.0 K, indicating the enhanced SMM behavior compared with 1-Dy . Ligand-based mixed-valency strategy has been used for the first time to improve the magnetic coupling in lanthanide (Ln) SMMs, thus opening up new ways to construct strongly coupled Ln-SMMs. 相似文献
53.
Dr. Shubham Dutta Dr. Rajendra K. Mallick Prof. Dr. Akhila K. Sahoo 《Angewandte Chemie (International ed. in English)》2023,62(30):e202300816
The use of ynamides in organic synthesis has gained significant attention due to their ability to provide access to complex molecular structures through transformations such as 1,2-difunctionalization and annulation reactions. These reactions enable the formation of highly functionalized N-bearing olefins and unusual N-bearing heterocycles. In this minireview, we present a systematic overview of the regioselective difunctionalization and annulation reactions of ynamides. We discuss the multi-component reactions, and radical-triggered functionalizations across the ynamides carbon–carbon multiple bonds and the use of bifunctional reagents in annulation of ynamides, highlighting their potential in expanding the substrate scope. Furthermore, we provide insights into the mechanistic breakthroughs that have been achieved in recent years in the development of these reactions. Finally, we emphasize the promising future prospects of ynamides as versatile building blocks for the synthesis of complex molecular architectures. 相似文献
54.
Peng-Zi Wang Prof. Dr. Wen-Jing Xiao Prof. Dr. Jia-Rong Chen 《Angewandte Chemie (International ed. in English)》2023,62(21):e202302227
Catalytic and switchable C−H functionalization of N-heteroarenes under easily tunable conditions is a robust but challenging tool for the construction of biologically relevant compounds. Recently, a general electrochemical strategy has been developed for the direct C−H carboxylation of N-heteroarenes with CO2, and by simply choosing different types of cell setups, carboxylated products are furnished with excellent and tunable site selectivity. This study also paves the way for regulating the reactivity modes in electrochemical synthesis. 相似文献
55.
Xiang Chen Dr. Shuhui Guan Jianjiang Zhou Hengjun Shang Jingyuan Zhang Fujian Lv Prof. Han Yu Prof. Dr. Hexing Li Prof. Zhenfeng Bian 《Angewandte Chemie (International ed. in English)》2023,62(45):e202312734
Single-atom catalysts (SACs) have emerged as crucial players in catalysis research, prompting extensive investigation and application. The precise control of metal atom nucleation and growth has garnered significant attention. In this study, we present a straightforward approach for preparing SACs utilizing a photocatalytic radical control strategy. Notably, we demonstrate for the first time that radicals generated during the photochemical process effectively hinder the aggregation of individual atoms. By leveraging the cooperative anchoring of nitrogen atoms and crystal lattice oxygen on the support, we successfully stabilize the single atom. Our Pd1/TiO2 catalysts exhibit remarkable catalytic activity and stability in the Suzuki–Miyaura cross-coupling reaction, which was 43 times higher than Pd/C. Furthermore, we successfully depose Pd atoms onto various substrates, including TiO2, CeO2, and WO3. The photocatalytic radical control strategy can be extended to other single-atom catalysts, such as Ir, Pt, Rh, and Ru, underscoring its broad applicability. 相似文献
56.
Antonio J. LaPorte Jack E. Feldner Jan C. Spies Tom J. Maher Prof. Martin D. Burke 《Angewandte Chemie (International ed. in English)》2023,62(40):e202309566
Multifunctional organoboron compounds increasingly enable the simple generation of complex, Csp3-rich small molecules. The ability of boron-containing functional groups to modify the reactivity of α-radicals has also enabled a myriad of chemical reactions. Boronic esters with vacant p-orbitals have a significant stabilizing effect on α-radicals due to delocalization of spin density into the empty orbital. The effect of coordinatively saturated derivatives, such as N-methyliminodiacetic acid (MIDA) boronates and counterparts, remains less clear. Herein, we demonstrate that coordinatively saturated MIDA and TIDA boronates stabilize secondary alkyl α-radicals via σB-N hyperconjugation in a manner that allows site-selective C−H bromination. DFT calculated radical stabilization energies and spin density maps as well as LED NMR kinetic analysis of photochemical bromination rates of different boronic esters further these findings. This work clarifies that the α-radical stabilizing effect of boronic esters does not only proceed via delocalization of radical character into vacant boron p-orbitals, but that hyperconjugation of tetrahedral boron-containing functional groups and their ligand electron delocalizing ability also play a critical role. These findings establish boron ligands as a useful dial for tuning reactivity at the α-carbon. 相似文献
57.
Mitchell D. Nothling John E. Daniels Yen Vo Ivan Johan Martina H. Stenzel 《Angewandte Chemie (International ed. in English)》2023,62(20):e202218955
Piezocatalysis offers a means to transduce mechanical energy into chemical potential, harnessing physical force to drive redox reactions. Working in the solid state, we show here that piezoelectric BaTiO3 nanoparticles can transduce mechanical load into a flux of reactive radical species capable of initiating solid state free radical polymerization. Activation of a BaTiO3 powder by ball milling, striking with a hammer, or repeated compressive loading generates highly reactive hydroxyl radicals (⋅OH), which readily initiate radical chain growth and crosslinking of solid acrylamide, acrylate, methacrylate and styrenic monomers. Control experiments indicate a critical role for chemisorbed water on the BaTiO3 nanoparticle surface, which is oxidized to ⋅OH via mechanoredox catalysis. The force-induced production of radicals by compressing dry piezoelectric materials represents a promising new route to harness mechanical energy for solid state radical synthesis. 相似文献
58.
Roman Bashkurov Dr. Alexander Kaushansky Dr. Boris Tumanskii Dr. Natalia Fridman Dr. Dmitry Bravo-Zhivotovskii Prof. Dr. Yitzhak Apeloig 《Angewandte Chemie (International ed. in English)》2023,62(18):e202300847
Thermolysis of a 1 : 1 mixture of tris(di-tert-butylmethylsilyl)germane 9 and bis(di-tert-butylmethylsilyl)germane 17 at 100 °C produces unexpectedly octagermacubane 18 , having two 3-coordinate Ge0 atoms (40 % yield). 18 was characterized by X-ray crystallography and it is a singlet biradical (according to DFT quantum mechanical calculations and the absence of an EPR signal). Reactions of 18 with CH2Cl2 and H2O yield the novel dichloro-octagermacubane 24 and hydroxy-octagermacubane 25 , respectively. Reduction of 18 with tBuMe2SiNa in THF produces an isolable octagermacubane radical anion 26-Na . Based on X-ray crystallography, EPR spectroscopy and DFT quantum mechanical calculations, 26-Na is classified as a Ge-centered radical anion. 相似文献
59.
Antioxidant and Prooxidant Nanozymes: From Cellular Redox Regulation to Next-Generation Therapeutics
Dr. Namrata Singh G. R. Sherin Prof. Dr. Govindasamy Mugesh 《Angewandte Chemie (International ed. in English)》2023,62(33):e202301232
Nanozymes, nanomaterials with enzyme-mimicking activity, have attracted tremendous interest in recent years owing to their ability to replace natural enzymes in various biomedical applications, such as biosensing, therapeutics, drug delivery, and bioimaging. In particular, the nanozymes capable of regulating the cellular redox status by mimicking the antioxidant enzymes in mammalian cells are of great therapeutic significance in oxidative-stress-mediated disorders. As the distinction of physiological oxidative stress (oxidative eustress) and pathological oxidative stress (oxidative distress) occurs at a fine borderline, it is a great challenge to design nanozymes that can differentially sense the two extremes in cells, tissues and organs and mediate appropriate redox chemical reactions. In this Review, we summarize the advances in the development of redox-active nanozymes and their biomedical applications. We primarily highlight the therapeutic significance of the antioxidant and prooxidant nanozymes in various disease model systems, such as cancer, neurodegeneration, and cardiovascular diseases. The future perspectives of this emerging area of research and the challenges associated with the biomedical applications of nanozymes are described. 相似文献