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101.
Weijie Yu Shengchun Wang Meng He Zhou Jiang Yi Yu Jinping Lan Jin Luo Pengjie Wang Prof. Xiaotian Qi Prof. Tao Wang Prof. Aiwen Lei 《Angewandte Chemie (International ed. in English)》2023,62(17):e202219166
Precisely introducing two similar functional groups into bulk chemical alkenes represents a formidable route to complex molecules. Especially, the selective activation of two electrophiles is in crucial demand, yet challenging for cross-electrophile-coupling. Herein, we demonstrate a redox-mediated electrolysis, in which aryl nitriles are both aryl radical precursors and redox-mediators, enables an intermolecular alkene 1,2-diarylation with a remarkable regioselectivity, thereby avoiding the involvement of transition-metal catalysts. This transformation utilizes cyanoarene radical anions for activating various aryl halides (including iodides, bromides, and even chlorides) and affords 1,2-diarylation adducts in up to 83 % yield and >20 : 1 regioselectivity with more than 80 examples, providing a feasible approach to complex bibenzyl derivatives. 相似文献
102.
Hui Luo Dr. Kejun Bu Dr. Yanfeng Yin Dong Wang Cuimi Shi Songhao Guo Tonghuan Fu Jiayuan Liang Bingyan Liu Dr. Dongzhou Zhang Prof. Liang-Jin Xu Prof. Qingyang Hu Prof. Yang Ding Prof. Shengye Jin Prof. Wenge Yang Prof. Biwu Ma Prof. Xujie Lü 《Angewandte Chemie (International ed. in English)》2023,62(37):e202304494
Low-dimensional (low-D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low-D OMHHs, especially the zero-D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near-unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C6H5)4P]2SbCl5. In situ experimental characterizations and theoretical simulations reveal that the pressure-induced electronic coupling between the lone-pair electrons of Sb3+ and the π electrons of benzene ring (lp-π interaction) serves as an unexpected “bridge” for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp-π interactions in organic–inorganic hybrid systems. 相似文献
103.
Keming Song Xiang Wang Zhengkun Xie Zhiwei Zhao Zhe Fang Zhengfeng Zhang Jun Luo Pengfei Yan Zhangquan Peng Weihua Chen 《Angewandte Chemie (International ed. in English)》2023,62(10):e202216450
Solid-electrolyte interphase (SEI) seriously affects battery's cycling life, especially for high-capacity anode due to excessive electrolyte decomposition from particle fracture. Herein, we report an ultrathin SEI (3–4 nm) induced by Cu+-tailored double electrical layer (EDL) to suppress electrolyte consumption and enhance cycling stability of CuS anode in sodium-ion batteries. Unique EDL with SO3CF3-Cu complex absorbing on CuS in NaSO3CF3/diglyme electrolyte is demonstrated by in situ surface-enhanced Raman, Cyro-TEM and theoretical calculation, in which SO3CF3-Cu could be reduced to CuF2-rich SEI. Dispersed CuF2 and F-containing compound can provide good interfacial contact for formation of ultrathin and stable SEI film to minimize electrolyte consumption and reduce activation energy of Na+ transport. As a result, the modified CuS delivers high capacity of 402.8 mAh g−1 after 7000 cycles without capacity decay. The insights of SEI construction pave a way for high-stability electrode. 相似文献
104.
Dr. Peng Luo Dr. Xue-Jing Zhai Dr. Sha Bai Dr. Yu-Bing Si Dr. Xi-Yan Dong Prof. Dr. Ying-Feng Han Prof. Dr. Shuang-Quan Zang 《Angewandte Chemie (International ed. in English)》2023,62(22):e202219017
Chiral Au nanoclusters have promising application prospects in chiral sensing, asymmetric catalysis, and chiroptics. However, enantiopure superatomic homogold clusters with crystallographic structures emitting bright circularly polarized luminescence (CPL) remain challenging. In this study, we designed chiral N-heterocyclic carbenes (NHCs), and for the first time enantioselectively synthesized a pair of monovalent cationic superatomic Au13 clusters. This new enantiomeric pair of clusters has a quasi-C2 symmetric core and exhibited CPL with an unprecedent solution-state quantum yield (QY) of 61 % among those of the atomically precise Au nanoclusters. DFT calculations provided insights into the circular dichroism behavior, and revealed the origin of CPL from superatomic Au clusters. This work opens a new avenue for developing novel homochiral nanoclusters using chiral NHC ligands and provides fundamental understanding of the origin of the chiroptics of metal clusters. 相似文献
105.
Yun-Cheng Luo Ming-Kuan Wang Ling-Chao Yu Prof. Dr. Xingang Zhang 《Angewandte Chemie (International ed. in English)》2023,62(37):e202308690
The selective transition-metal catalyzed C−F bond functionalization of inexpensive industrial fluorochemicals represents one of the most attractive approaches to valuable fluorinated compounds. However, the selective C(sp2)−F bond carbofunctionalization of refrigerant hydrofluoroolefins (HFOs) remains challenging. Here, we report a nickel-catalyzed selective C(sp2)−F bond alkylation of HFO-1234yf with alkylzinc reagents. The resulting 2-trifluoromethylalkenes can serve as a versatile synthon for diversified transformations, including the anti-Markovnikov type hydroalkylation and the synthesis of bioactive molecule analogues. Mechanistic studies reveal that lithium salt is essential to promote the oxidative addition of Ni0(Ln) to the C−F bond; the less electron-rich N-based ligands, such as bipyridine and pyridine-oxazoline, feature comparable or even higher oxidative addition rates than the electron-rich phosphine ligands; the strong σ-donating phosphine ligands, such as PMe3, are detrimental to transmetallation, but the less electron-rich and bulky N-based ligands, such as pyridine-oxazoline, facilitate transmetallation and reductive elimination to form the final product. 相似文献
106.
Dr. Jiancheng Luo Dr. Xiao Zhao Hao Ju Dr. Xiangjun Chen Dr. Sheng Zhao Dr. Zoriana Demchuk Dr. Bingrui Li Dr. Vera Bocharova Dr. Jan-Michael Y. Carrillo Dr. Jong K. Keum Prof. Sheng Xu Prof. Alexei P. Sokolov Dr. Jiayao Chen Prof. Peng-Fei Cao 《Angewandte Chemie (International ed. in English)》2023,62(47):e202310989
Despite intensive research on sustainable elastomers, achieving elastic vitrimers with significantly improved mechanical properties and recyclability remains a scientific challenge. Herein, inspired by the classical elasticity theory, we present a design principle for ultra-tough and highly recyclable elastic vitrimers with a defined network constructed by chemically crosslinking the pre-synthesized disulfide-containing polydimethylsiloxane (PDMS) chains with tetra-arm polyethylene glycol (PEG). The defined network is achieved by the reduced dangling short chains and the relatively uniform molecular weight of network strands. Such elastic vitrimers with the defined network, i.e., PDMS-disulfide-D, exhibit significantly improved mechanical performance than random analogous, previously reported PDMS vitrimers, and even commercial silicone-based thermosets. Moreover, unlike the vitrimers with random network that show obvious loss in mechanical properties after recycling, those with the defined network enable excellent thermal recyclability. The PDMS-disulfide-D also deliver comparable electrochemical signals if utilized as substrates for electromyography sensors after the recycling. The multiple relaxation processes are revealed via a unique physical approach. Multiple techniques are also applied to unravel the microscopic mechanism of the excellent mechanical performance and recyclability of such defined network. 相似文献
107.
Dr. Sarah Desmons Yu Zhou Dr. Dan Zhang Dr. Carlos Jarava-Barrera Dr. Anaïs Coffinet Dr. Antoine Simonneau Dr. Laure Vendier Prof. Dr. Gen Luo Dr. Sébastien Bontemps 《European journal of organic chemistry》2023,26(30):e202300525
The hydroboration of CO2 into bis(boryl)acetal (BBA) compounds is an important transformation, since it enabled to selectively reduce CO2 by 4e- and to subsequently use the BBA compounds as C1 and Cn sources. However, the influence of the nature of the boryl moieties on the reactivity of BBA compounds has not been evaluated so far. In the present study, four BBA compounds – including two new ones – were reacted with 2,6-diisopropylaniline to afford the expected imine. Significant differences in the rate of the reaction from minutes to weeks have been observed depending on the BBA used, showing the importance of the nature of the boryl moieties. Theoretical investigations enabled to propose a mechanism involving the addition of the aniline to the BBA as the rate-determining step and to determine that the steric hindrance of the BBA compounds is the main factor driving the rate of this condensation reaction. 相似文献
108.
Sai Luo Junjie Wang Dr. Nengquan Li Dr. Xiu-Fang Song Xintong Wan Prof. Dr. Kai Li Prof. Dr. Chuluo Yang 《Angewandte Chemie (International ed. in English)》2023,62(49):e202310943
B- and N-embedded multiple resonance (MR) type thermally activated delayed fluorescence (TADF) emitters usually suffer from slow reverse intersystem crossing (RISC) process and aggregation-caused emission quenching. Here, we report the design of a sandwich structure by placing the B−N MR core between two electron-donating moieties, inducing through-space charge transfer (TSCT) states. The proper adjusting of the energy levels brings about a 10-fold higher RISC rate in comparison with the parent B−N molecule. In the meantime, a high photoluminescence quantum yield of 91 % and a good color purity were maintained. Organic light-emitting diodes based on the new MR emitter achieved a maximum external quantum efficiency of 31.7 % and small roll-offs at high brightness. High device efficiencies were also obtained for a wide range of doping concentrations of up to 20 wt % thanks to the steric shielding of the B−N core. A good operational stability with LT95 of 85.2 h has also been revealed. The dual steric and electronic effects resulting from the introduction of a TSCT state offer an effective molecular design to address the critical challenges of MR-TADF emitters. 相似文献
109.
Yicong Luo Yuqi Ma Guanlin Li Xiaohong Huo Wanbin Zhang 《Angewandte Chemie (International ed. in English)》2023,62(47):e202313838
Fluorinated amino acids and related peptides/proteins have been found widespread applications in pharmaceutical and agricultural compounds. However, strategies for introducing a C−F bond into amino acids in an enantioselective manner are still limited and no such asymmetric catalysis strategy has been reported. Herein, we have successfully developed a Pd/Cu/Li ternary system for stereodivergent synthesis of chiral fluorinated amino acids. This method involves a sequential desymmetrization of geminal difluoromethylenes and allylic substitution with amino acid Schiff bases via Pd/Li and Pd/Cu dual activation, respectively. A series of non-natural amino acids bearing a chiral allylic/benzylic fluorine motif are easily synthesized in high yields with excellent regio-, diastereo-, and enantioselectivities (up to >20 : 1 dr and >99 % ee). A density functional theory (DFT) study revealed the F−Cu interaction of the allylic substrate and the Cu catalyst significantly influence the stereoselectivity. 相似文献
110.
Dr. Chi Zhang Dr. Meiling Shao Dr. Dongqing Wu Dr. Zhongyi Li Muzhi Zhao Xiangfei Zhang Prof. Bin Zhai Prof. Yunjun Luo Prof. Xiaoyu Li 《Angewandte Chemie (International ed. in English)》2023,62(52):e202314052
Azide compounds are widely used and especially, polymers bearing pendant azide groups are highly desired in numerous fields. However, harsh reaction conditions are always mandatory to achieve full azidation, causing severe side reactions and degradation of the polymers. Herein, we report the design and preparation of two azide ionic liquids (AILs) with azide anion and triethylene glycol (E3)-containing cation, [P444E3][N3] and [MIME3][N3]. Compared with the traditional sodium azide (NaN3) approach, both AILs showed much higher reaction rates and functional-group tolerance. More importantly, they could act as both reagents and solvents for the quantitative azidation of various polymeric precursors under mild conditions. Theoretical simulations suggested that the outstanding performance of AILs originated from the existence of ion pairs during the reaction, and the E3 moieties played a crucial role. Lastly, after the reaction, the AILs could be easily regenerated, presenting a safer, greener, and highly efficient synthesis route for azide polymers. 相似文献