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991.
Wei Shyang Tan Ting‐Yin Lee Sheng‐Fang Tseng Ying‐Feng Hsu Masanori Ebina Tetsuya Taketsugu Shing‐Jong Huang Jye‐Shane Yang 《中国化学会会志》2019,66(9):1141-1156
Despite the long history of polyaniline chemistry, backbone‐substituted polyanilines are limited. Here, we report the synthesis of pentiptycene‐incorporated polyanilines through acidic aniline oxidative polymerization with three pentiptycene derivatives, TA, DA, and TP, as nucleate additives. The reactivity of TA > DA ? TP, as evidenced by structural and property analysis of the corresponding polyaniline products, demonstrates a radical coupling mechanism and the formation of Dewar π‐complex intermediates for the chain propagation. In addition, the iptycene substituent effect on enhancing the electrochemical stability and charge storage capability of polyaniline are discussed with a clip model, namely, the threading of neighboring polyaniline chains through the U‐ and V‐shaped cavities of pentiptycene restricts lateral motions of the polymer chains and promotes interchain conductivity. Density function theory (DFT) calculations suggest a larger clipping effect for the U versus V cavities. Both the conclusion of a terminal planar p‐phenylenediamine (ppda) group being the key component of an effective nucleate and the concept of interchain clipping for enhanced electrochemical performance should facilitate the design and synthesis of novel polyanilines for electronic applications. 相似文献
992.
Diaportheone A (1), a chromone natural product was previously isolated from the endophytic fungi Diaporthe sp. P 133. Its structure was established by spectroscopic methods, however, its absolute configuration remained undefined. This study dealt on the total synthesis of diaportheone A (1) utilizing the cyclization and in situ thermal syn-elimination of a β-ketosulfoxide. The C-1R absolute configuration of the natural product was established by X-ray crystallography of the synthetic diaportheone A (1) (>99%?ee) and comparison with the optical rotation. 相似文献
993.
994.
Shuning Cai Wenting Deng Feifei Huang Lijue Chen Chun Tang Wenxiang He Shichuan Long Ruihao Li Zhibing Tan Junyang Liu Jia Shi Zitong Liu Zongyuan Xiao Deqing Zhang Wenjing Hong 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(12):3869-3873
Photoresponsive molecular systems are essential for molecular optoelectronic devices, but most molecular building blocks are non‐photoresponsive. Employed here is a photoinduced proton transfer (PIPT) strategy to control charge transport through single‐molecule azulene junctions with visible light under ambient conditions, which leads to a reversible and controllable photoresponsive molecular device based on non‐photoresponsive molecules and a photoacid. Also demonstrated is the application of PIPT in two single‐molecule AND gate and OR gate devices with electrical signal as outputs. 相似文献
995.
Jianke Pan Jia‐Hong Wu Hongkui Zhang Xiaoyu Ren Jian‐Ping Tan Lixiang Zhu Hong‐Su Zhang Chunhui Jiang Tianli Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(22):7503-7508
The first enantioselective aza‐Darzens reaction of cyclic imines with α‐halogenated ketones was realized under mild reaction conditions by using amino‐acid‐derived bifunctional phosphonium salts as phase‐transfer promoters. A variety of structurally dense tri‐ and tetrasubstituted aziridine derivatives, containing benzofused heterocycles as well as spiro‐structures, were readily synthesized in high yields with excellent diastereo‐ and enantioselectivities (up to >20:1 d.r. and >99.9 % ee). The highly functionalized aziridine products could be easily transformed into different classes of biologically active compounds. 相似文献
996.
Wenhao Ren Xin Tan Wanfeng Yang Chen Jia Shumao Xu Kaixue Wang Sean C. Smith Chuan Zhao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(21):7046-7050
Polynary single‐atom structures can combine the advantages of homogeneous and heterogeneous catalysts while providing synergistic functions based on different molecules and their interfaces. However, the fabrication and identification of such an active‐site prototype remain elusive. Here we report isolated diatomic Ni‐Fe sites anchored on nitrogenated carbon as an efficient electrocatalyst for CO2 reduction. The catalyst exhibits high selectivity with CO Faradaic efficiency above 90 % over a wide potential range from ?0.5 to ?0.9 V (98 % at ?0.7 V), and robust durability, retaining 99 % of its initial selectivity after 30 hours of electrolysis. Density functional theory studies reveal that the neighboring Ni‐Fe centers not only function in synergy to decrease the reaction barrier for the formation of COOH* and desorption of CO, but also undergo distinct structural evolution into a CO‐adsorbed moiety upon CO2 uptake. 相似文献
997.
Rui Feng Li Zhang Huapeng Ruan Yue Zhao Gengwen Tan Xinping Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(18):6145-6149
The first main‐group element radical based one‐dimensional magnetic chain ( 1K )n was realized by one‐electron reduction of the pyridinyl functionalized borane 1 with elemental potassium in THF in the absence of 18‐crown‐6 (18‐c‐6). The electron spin density of ( 1K )n mainly resides at the boron centers with a considerable contribution from central benzene and pyridine moieties. The spin centers exhibit an antiferromagnetic interaction as demonstrated by magnetic measurements and theoretical calculations. In contrast, the reduction in the presence of 18‐c‐6 afforded the separated radical anion salt 1K(Crown) , in which the potassium cation was trapped by THF and 18‐c‐6 molecules. Further one‐electron reduction of 1K(Crown) and ( 1K )n led to the diamagnetic monomer and polymer, respectively. 相似文献
998.
Qiuyuan Tan Zhao Yang Dan Jiang Yuegang Cheng Jiao Yang Song Xi Min Zhang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(19):6486-6490
Based on the discovery of copper‐catalyzed cyclopropanol ring‐opening addition to iminium ions, an unprecedented catalytic aerobic C?H oxidation/cyclopropanol cyclization cascade using CuCl2 as the multifunctional catalyst and air as the oxidant was developed to construct the azabicyclo[3.3.1]nonane skeleton, which is widespread in natural products and medicines. Using this method, concise asymmetric total synthesis of the indole alkaloid (?)‐suaveoline was achieved. This study not only provides an efficient, low‐cost, and environmentally benign method for constructing such bridged frameworks, but also enriches the realm of cyclopropanol chemistry and C?H functionalization. 相似文献
999.
1000.
Yu‐Min Liu Yu‐Qian Huang Shun‐He Liu Dandan Chen Chun Tang Zhen‐Lin Qiu Jun Zhu Yuan‐Zhi Tan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(38):13410-13413
Bowl inversion is a unique property of buckybowls. The polarity and assembly configuration of buckybowls are reversed after bowl inversion. So far, this unique phenomenon has been studied in solution and on surface, but not in solid state due to spatial constraint. Now a series of exo‐type supramolecular assemblies of trithiasumanene and nanographene are investigated. Tuning the electron density of the nanogaphene component was found to directly affect the binding constant of the complex. Reversible bowl inversion in the solid state was then successfully achieved by subjecting the trithiasumanene–nanographene assembly with the weakest binding strength to repeated heating–cooling cycles, which was unambiguously observed by single crystal X‐ray diffraction. 相似文献