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981.
Yang Li Yuan‐Yuan An Jian‐Zhong Fan Xiao‐Xu Liu Xin Li F. Ekkehardt Hahn Yao‐Yu Wang Ying‐Feng Han 《Angewandte Chemie (International ed. in English)》2020,59(25):10073-10080
A series of supramolecular assemblies of types [Ag8( L )4](PF6)8 and [Ag4( L )2](PF6)4, obtained from the tetraphenylethylene (TPE) bridged tetrakis(1,2,4‐triazolium) salts H4‐L(PF6)4 and AgI ions, is described. The assembly type obtained dependends on the N‐wingtip substituents of H4‐L(PF6)4. Changes in the lengths of the N4‐wingtip substituents enables controlled formation of assemblies with either [Ag4( L )2](PF6)4 or [Ag8( L )4](PF6)8 stoichiometry. The molecular structures of selected [Ag8( L )4](PF6)8 and [Ag4( L )2](PF6)4 assemblies were determined by X‐ray diffraction analyses. While H4‐ L (PF6)4 does not exhibit fluorescence in solution, their tetra‐NHC (NHC=N‐heterocyclic carbene) assemblies do upon NHC–metal coordination. Upon irradiation, all assemblies undergo a light‐induced, supramolecule‐to‐supramolecule structural transformation by an oxidative photocyclization involving phenyl groups of the TPE core, resulting in a significant change of the luminescence properties. 相似文献
982.
Tianyi Song Wenjiao Yao Pinit Kiadkhunthod Yongping Zheng Nanzhong Wu Xiaolong Zhou Sarayut Tunmee Suchinda Sattayaporn Yongbing Tang 《Angewandte Chemie (International ed. in English)》2020,59(2):740-745
Sodium‐ion batteries (NIBs) are the most promising alternatives to lithium‐ion batteries in the development of renewable energy sources. The advancement of NIBs depends on the exploration of new electrode materials and fundamental understanding of working mechanisms. Herein, via experimental and simulation methods, we develop a mixed polyanionic compound, Na2Fe(C2O4)SO4?H2O, as a cathode for NIBs. Thanks to its rigid three dimensional framework and the combined inductive effects from oxalate and sulfate, it delivered reversible Na insertion/desertion at average discharging voltages of 3.5 and 3.1 V for 500 cycles with Coulombic efficiencies of ca. 99 %. In situ synchrotron X‐ray measurements and DFT calculations demonstrate the Fe2+/Fe3+ redox reactions contribute to electron compensation during Na+ desertion/insertion. The study suggests mixed polyanionic frameworks may provide promising materials for Na ion storage with the merits of low cost and environmental friendliness. 相似文献
983.
Chao Wang Qinglong Qiao Weijie Chi Jie Chen Wenjuan Liu Davin Tan Scott McKechnie Da Lyu Xiao‐Fang Jiang Wei Zhou Ning Xu Qisheng Zhang Zhaochao Xu Xiaogang Liu 《Angewandte Chemie (International ed. in English)》2020,59(25):10160-10172
Inhibition of TICT can significantly increase the brightness of fluorescent materials. Accurate prediction of TICT is thus critical for the quantitative design of high‐performance fluorophores and AIEgens. TICT of 14 types of popular organic fluorophores were modeled with time‐dependent density functional theory (TD‐DFT). A reliable and generalizable computational approach for modeling TICT formations was established. To demonstrate the prediction power of our approach, we quantitatively designed a boron dipyrromethene (BODIPY)‐based AIEgen which exhibits (almost) barrierless TICT rotations in monomers. Subsequent experiments validated our molecular design and showed that the aggregation of this compound turns on bright emissions with ca. 27‐fold fluorescence enhancement, as TICT formation is inhibited in molecular aggregates. 相似文献
984.
Ming Zhu Guanyao Wang Xing Liu Bingkun Guo Gang Xu Zhongyi Huang Minghong Wu Hua‐Kun Liu Shi‐Xue Dou Chao Wu 《Angewandte Chemie (International ed. in English)》2020,59(16):6596-6600
Sodium metal is an ideal anode material for metal rechargeable batteries, owing to its high theoretical capacity (1166 mAh g?1), low cost, and earth‐abundance. However, the dendritic growth upon Na plating, stemming from unstable solid electrolyte interphase (SEI) film, is a major and most notable problem. Here, a sodium benzenedithiolate (PhS2Na2)‐rich protection layer is synthesized in situ on sodium by a facile method that effectively prevents dendrite growth in the carbonate electrolyte, leading to stabilized sodium metal electrodeposition for 400 cycles (800 h) of repeated plating/stripping at a current density of 1 mA cm?2. The organic salt, PhS2Na2, is found to be a critical component in the protection layer. This finding opens up a new and promising avenue, based on organic sodium slats, to stabilize sodium metals with a protection layer. 相似文献
985.
Zhennan Wu Qiaofeng Yao Osburg Jin Huang Chai Nan Ding Wen Xu Shuangquan Zang Jianping Xie 《Angewandte Chemie (International ed. in English)》2020,59(25):9934-9939
Aggregation‐induced emission (AIE) provides an efficient strategy to synthesize highly luminescent metal nanoclusters (NCs), however, rational control of emission energy and intensity of metal NCs is still challenging. This communication reveals the impact of surface AuI‐thiolate motifs on the AIE properties of Au NCs, by employing a series of water‐soluble glutathione (GSH)‐coordinated Au complexes and NCs as a model ([Au10SR10], [Au15SR13], [Au18SR14], and [Au25SR18]?, SR=thiolate ligand). Spectroscopic investigations show that the emission wavelength of Au NCs is adjustable from visible to the near‐infrared II (NIR‐II) region by controlling the length of the AuI‐SR motifs on the NC surface. Decreasing the length of AuI‐SR motifs also changes the origin of cluster luminescence from AIE‐type phosphorescence to Au0‐core‐dictated fluorescence. This effect becomes more prominent when the degree of aggregation of Au NCs increases in solution. 相似文献
986.
Wen‐Chao Geng Dongmei Zhang Chu Gong Zhihao Li Kevin M. Barraza Jesse L. Beauchamp Dong‐Sheng Guo Xinxing Zhang 《Angewandte Chemie (International ed. in English)》2020,59(31):12684-12688
The oxidation of antioxidants by oxidizers imposes great challenges to both living organisms and the food industry. Here we show that the host–guest complexation of the carefully designed, positively charged, amphiphilic guanidinocalix[5]arene pentadodecyl ether (GC5A‐12C) and negatively charged oleic acid (OA), a well‐known cell membrane antioxidant, prevents the oxidation of the complex monolayers at the air–water interface from two potent oxidizers hydroxyl radicals (OH) and singlet delta oxygen (SDO). OH is generated from the gas phase and attacks from the top of the monolayer, while SDO is generated inside the monolayer and attacks amphiphiles from a lateral direction. Field‐induced droplet ionization mass spectrometry results have demonstrated that the host–guest complexation achieves steric shielding and prevents both types of oxidation as a result of the tight and “sleeved in” physical arrangement, rather than the chemical reactivity, of the complexes. 相似文献
987.
Jie Yang Xiao‐Ming Zhang Fu‐Min Zhang Shao‐Hua Wang Yong‐Qiang Tu Zhen Li Xi‐Chao Wang Hong Wang 《Angewandte Chemie (International ed. in English)》2020,59(22):8471-8475
An enantioselective aldehyde α‐alkylation/semipinacol rearrangement was achieved through organo‐SOMO catalysis. The catalytically generated enamine radical cation serves as a carbon radical electrophile that can stereoselectively add to the alkene of an allylic alcohol and initiate ensuing ring‐expansion of cyclopropanol or cyclobutanol. This tandem reaction enables the production of a wide range of nonracemic functionalizable α‐quaternary‐δ‐carbonyl cycloketones in high yields and excellent enantioselectivity from simple aldehydes and allylic alcohols. As a key step, the intramolecular reaction was also successfully applied in the asymmetric total synthesis of (+)‐cerapicol. 相似文献
988.
Chao Wang Min Hu Yueying Chu Xue Zhou Qiang Wang Guodong Qi Shenhui Li Jun Xu Feng Deng 《Angewandte Chemie (International ed. in English)》2020,59(18):7198-7202
The understanding of catalyst deactivation represents one of the major challenges for the methanol‐to‐hydrocarbon (MTH) reaction over acidic zeolites. Here we report the critical role of intermolecular π‐interactions in catalyst deactivation in the MTH reaction on zeolites H‐SSZ‐13 and H‐ZSM‐5. π‐interaction‐induced spatial proximities between cyclopentenyl cations and aromatics in the confined channels and/or cages of zeolites are revealed by two‐dimensional solid‐state NMR spectroscopy. The formation of naphtalene as a precursor to coke species is favored due to the reaction of aromatics with the nearby cyclopentenyl cations and correlates with both acid density and zeolite topology. 相似文献
989.
Haidong Li Qichao Yao Feng Xu Yueqing Li Dayeh Kim Jeewon Chung Gain Baek Xiaofeng Wu Prima Fitria Hillman Eun Young Lee Haoying Ge Jiangli Fan Jingyun Wang Sang‐Jip Nam Xiaojun Peng Juyoung Yoon 《Angewandte Chemie (International ed. in English)》2020,59(25):10186-10195
Monitoring fluctuations in enzyme overexpression facilitates early tumor detection and excision. An AIEgen probe (DQM‐ALP) for the imaging of alkaline phosphatase (ALP) activity was synthesized. The probe consists of a quinoline‐malononitrile (QM) core decorated with hydrophilic phosphate groups as ALP‐recognition units. The rapid liberation of DQM‐OH aggregates in the presence of ALP resulted in aggregation‐induced fluorescence. The up‐regulation of ALP expression in tumor cells was imaged using DQM‐ALP. The probe permeated into 3D cervical and liver tumor spheroids for imaging spatially heterogeneous ALP activity with high spatial resolution on a two‐photon microscopy platform, providing the fluorescence‐guided recognition of sub‐millimeter tumorigenesis. DQM‐ALP enabled differentiation between tumor and normal tissue ex vivo and in vivo, suggesting that the probe may serve as a powerful tool to assist surgeons during tumor resection. 相似文献
990.
Xing‐Ben Wang Zhan‐Jiang Zheng Jia‐Le Xie Xing‐Wei Gu Qiu‐Chao Mu Guan‐Wu Yin Fei Ye Zheng Xu Li‐Wen Xu 《Angewandte Chemie (International ed. in English)》2020,59(2):790-797
A novel and unusual palladium‐catalyzed [4+2] annulation of cyclopropenes with benzosilacyclobutanes is reported. This reaction occurred through chemoselective Si?C(sp2) bond activation in synergy with ring expansion/insertion of cyclopropenes to form new C(sp2)?C(sp3) and Si?C(sp3) bonds. An array of previously elusive bicyclic skeleton with high strain, silabicyclo[4.1.0]heptanes, were formed in good yields with excellent diastereoselectivity under mild conditions. An asymmetric version of the reaction with a chiral phosphoramidite ligand furnished a variety of chiral bicyclic silaheterocycle derivatives with good enantioselectivity (up to 95.5:4.5 er). Owing to the mild reaction conditions, the good stereoselectivity profile, and the ready availability of the functionalized precursors, this process constitutes a useful and straightforward strategy for the synthesis of densely functionalized silacycles. 相似文献