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991.
Jingjuan Liu Yi Zhou Zhen Xie Yang Li Yunpeng Liu Jie Sun Yanhang Ma Osamu Terasaki Long Chen 《Angewandte Chemie (International ed. in English)》2020,59(3):1081-1086
A conjugated copper(II) catecholate based metal–organic framework (namely Cu‐DBC) was prepared using a D2‐symmetric redox‐active ligand in a copper bis(dihydroxy) coordination geometry. The π‐d conjugated framework exhibits typical semiconducting behavior with a high electrical conductivity of ca. 1.0 S m?1 at room temperature. Benefiting from the good electrical conductivity and the excellent redox reversibility of both ligand and copper centers, Cu‐DBC electrode features superior capacitor performances with gravimetric capacitance up to 479 F g?1 at a discharge rate of 0.2 A g?1. Moreover, the symmetric solid‐state supercapacitor of Cu‐DBC exhibits high areal (879 mF cm?2) and volumetric (22 F cm?3) capacitances, as well as good rate capability. These metrics are superior to most reported MOF‐based supercapacitors, demonstrating promising applications in energy‐storage devices. 相似文献
992.
Ross F. Koby Alicia M. Doerr Nicholas R. Rightmire Nathan D. Schley Brian K. Long Timothy P. Hanusa 《Angewandte Chemie (International ed. in English)》2020,59(24):9542-9548
Milling two equivalents of K[1,3‐(SiMe3)2C3H3] (=K[A′]) with MgX2 (X=Cl, Br) produces the allyl complex [K2MgA′4] ( 1 ). Crystals grown from toluene are of the solvated species [((η6‐tol)K)2MgA′4] ([ 1 ?2(tol)]), a trimetallic monomer with both bridging and terminal (η1) allyl ligands. When recrystallized from hexanes, the unsolvated 1 forms a 2D coordination polymer, in which the Mg is surrounded by three allyl ligands. The C?C bond lengths differ by only 0.028 Å, indicating virtually complete electron delocalization. This is an unprecedented coordination mode for an allyl ligand bound to Mg. DFT calculations indicate that in isolation, an η3‐allyl configuration on Mg is energetically preferred over the η1‐ (σ‐bonded) arrangement, but the Mg must be in a low coordination environment for it to be experimentally realized. Methyl methacrylate is effectively polymerized by 1 , with activities that are comparable to K[A′] and greater than the homometallic magnesium complex [{MgA′2}2]. 相似文献
993.
Huixin Fan Chensheng Lin Kaichuang Chen Guang Peng Bingxuan Li Ge Zhang Xifa Long Ning Ye 《Angewandte Chemie (International ed. in English)》2020,59(13):5268-5272
An ammonium‐containing metal iodate fluoride compound, (NH4)Bi2(IO3)2F5, featuring a two‐dimensional double‐layered framework constructed by [BiO2F5]6? and [BiO4F4]9? polyhedra, as well as [IO3]? groups, was successfully synthesized. The well‐ordered alignment of these SHG‐active units leads to an extraordinary strong SHG response of 9.2 times that of KDP. Moreover, this compound possesses a large birefringence (Δn=0.0690 at 589.3 nm), a wide energy band gap (Eg=3.88 eV), and a high laser damage threshold (LDT; 40.2×AgGaS2). In particular, thermochromic behavior was observed for the first time in this type of compound. Such multifunctional crystals will expand the application of nonlinear optical materials. 相似文献
994.
Long Yang Ralf Steinbock Alexej Scheremetjew Rositha Kuniyil Lars H. Finger Antonis M. Messinis Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2020,59(27):11130-11135
A ruthenium‐catalyzed electrochemical dehydrogenative annulation reaction of imidazoles with alkynes has been established, enabling the preparation of various bridgehead N‐fused [5,6]‐bicyclic heteroarenes through regioselective electrochemical C?H/N?H annulation without chemical metal oxidants. Novel azaruthenabicyclo[3.2.0]heptadienes were fully characterized and identified as key intermediates. Mechanistic studies are suggestive of an oxidatively induced reductive elimination pathway within a ruthenium(II/III) regime. 相似文献
995.
Polyether Natural Product Inspired Cascade Cyclizations: Autocatalysis on π‐Acidic Aromatic Surfaces
Miguel Paraja Xiaoyu Hao Stefan Matile 《Angewandte Chemie (International ed. in English)》2020,59(35):15093-15097
Anion‐π catalysis functions by stabilizing anionic transition states on aromatic π surfaces, thus providing a new approach to molecular transformation. The delocalized nature of anion–π interactions suggests that they serve best in stabilizing long‐distance charge displacements. Aiming therefore for an anionic cascade reaction that is as charismatic as the steroid cyclization is for conventional cation‐π biocatalysis, reported here is the anion‐π‐catalyzed epoxide‐opening ether cyclizations of oligomers. Only on π‐acidic aromatic surfaces having a positive quadrupole moment, such as hexafluorobenzene to naphthalenediimides, do these polyether cascade cyclizations proceed with exceptionally high autocatalysis (rate enhancements kauto/kcat >104 m ?1). This distinctive characteristic adds complexity to reaction mechanisms (Goldilocks‐type substrate concentration dependence, entropy‐centered substrate destabilization) and opens intriguing perspectives for future developments. 相似文献
996.
Ji‐Long Shi Rufan Chen Huimin Hao Cheng Wang Xianjun Lang 《Angewandte Chemie (International ed. in English)》2020,59(23):9088-9093
2D covalent organic frameworks (COFs) are receiving ongoing attention in semiconductor photocatalysis. Herein, we present a photocatalytic selective chemical transformation by combining sp2 carbon‐conjugated porphyrin‐based covalent organic framework (Por‐sp2c‐COF) photocatalysis with TEMPO catalysis illuminated by 623 nm red light‐emitting diodes (LEDs). Highly selective conversion of amines into imines was swiftly afforded in minutes. Specifically, the π‐conjugation of porphyrin linker leads to extensive absorption of red light; the sp2 ?C=C? double bonds linkage ensures the stability of Por‐sp2c‐COF under high concentrations of amine. Most importantly, we found that crystalline framework of Por‐sp2c‐COF is pivotal for cooperative photocatalysis with (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO). This work foreshadows that the outstanding hallmarks of COFs, particularly crystallinity, could be exploited to address energy and environmental challenges by cooperative photocatalysis. 相似文献
997.
Long Zhao Ralf I. Kaiser Bo Xu Utuq Ablikim Musahid Ahmed Mikhail M. Evseev Eugene K. Bashkirov Valeriy N. Azyazov Alexander M. Mebel 《Angewandte Chemie (International ed. in English)》2020,59(10):4051-4058
A unified low‐temperature reaction mechanism on the formation of acenes, phenacenes, and helicenes—polycyclic aromatic hydrocarbons (PAHs) that are distinct via the linear, zigzag, and ortho‐condensed arrangements of fused benzene rings—is revealed. This mechanism is mediated through a barrierless, vinylacetylene mediated gas‐phase chemistry utilizing tetracene, [4]phenacene, and [4]helicene as benchmarks contesting established ideas that molecular mass growth processes to PAHs transpire at elevated temperatures. This mechanism opens up an isomer‐selective route to aromatic structures involving submerged reaction barriers, resonantly stabilized free‐radical intermediates, and systematic ring annulation potentially yielding molecular wires along with racemic mixtures of helicenes in deep space. Connecting helicene templates to the Origins of Life ultimately changes our hypothesis on interstellar carbon chemistry. 相似文献
998.
Peng‐Ju Xia Dan Song Zhi‐Peng Ye Yuan‐Zhuo Hu Jun‐An Xiao Hao‐Yue Xiang Xiao‐Qing Chen Hua Yang 《Angewandte Chemie (International ed. in English)》2020,59(17):6706-6710
A photoinduced SET process enables the direct B?H bond activation of NHC–boranes. In contrast to common hydrogen atom transfer (HAT) strategies, this photoinduced reaction simply takes advantage of the beneficial redox potentials of NHC–boranes, thus obviating the need for extra radical initiators. The resulting NHC–boryl radical was used for the borylation of a wide range of α‐trifluoromethylalkenes and alkenes with diverse electronic and structural features, providing facile access to highly functionalized borylated molecules. Labeling and photoquenching experiments provide insight into the mechanism of this photoinduced SET pathway. 相似文献
999.
1000.
A novel fluorinated chain extender, (1‐(ethyl(2‐hydroxyethyl)amino)‐3‐ ((3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl)oxy)propan‐2‐ol) (FPO), was synthesized and characterized by nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), and elemental analysis. Poly (ether urethane)s containing various amounts of the chain extender with fluorinated side chains (FPUs) were prepared by isophorone diisocyanate (IPDI), polytetra‐methylene‐ether‐glycol (PTMG), 3‐aminopropyltriethoxysilane (KH‐550), and 1,4‐butandiol (BDO). Films of FPUs were investigated by water absorption, contact angle, pencil hardness, adhesive force, and thermal analysis. Coating FPUs on micro‐nano concave‐convex structure plate realizes superhydrophobic performance. Scanning electron microscope (SEM) and atomic force microscopy (AFM) demonstrated that there is a lot of irregular concave‐convex structure, which forms a typical air cushion model. X‐ray photoelectron spectroscopy (XPS) analysis showed that surface fluorine content is 165% more than that of film average fluorine content. The superhydrophobic plate with 10% or higher F‐containing FPUs coating is of outstanding chemical corrosion resistance, excellent solvent resistance, and wear resistance. 相似文献