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91.
Zhongchao Jin Dr. Xiaorong Zhu Dr. Ningning Wang Prof. Dr. Yafei Li Prof. Dr. Huangxian Ju Prof. Dr. Jianping Lei 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(26):10532-10536
Metal–organic frameworks (MOFs) have limited applications in electrochemistry owing to their poor conductivity. Now, an electroactive MOF (E-MOF) is designed as a highly crystallized electrochemiluminescence (ECL) emitter in aqueous medium. The E-MOF contains mixed ligands of hydroquinone and phenanthroline as oxidative and reductive couples, respectively. E-MOFs demonstrate excellent performance with surface state model in both co-reactant and annihilation ECL in aqueous medium. Compared with the individual components, E-MOFs significantly improve the ECL emission due to the framework structure. The self-enhanced ECL emission with high stability is realized by the accumulation of MOF cation radicals via pre-reduction electrolysis. The self-enhanced mechanism is theoretically identified by DFT. The mixed-ligand E-MOFs provide a proof of concept using molecular crystalline materials as new ECL emitters for fundamental mechanism studies. 相似文献
92.
Dr. Hui Chen Lei Shi Xiao Liang Lina Wang Prof. Tewodros Asefa Prof. Xiaoxin Zou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(44):19822-19826
Reducing the amount of iridium in oxygen evolution electrocatalysts without compromising their catalytic performances is one of the major requirements in proton-exchange-membrane water electrolyzers. Herein, with the help of theoretical studies, we show that anatase-type TiO2-IrO2 solid solutions possess more active iridium catalytic sites for the oxygen evolution reaction (OER) than IrO2, the benchmark OER catalyst. Note that the same is not observed for their rutile-type counterparts. However, owing to their thermodynamic metastability, anatase-type TiO2-IrO2 solid solutions are generally hard to synthesize. Our theoretical studies demonstrate that such catalytically active anatase-type solid-solution phases can be created in situ on the surfaces of readily available SrTiO3-SrIrO3 solid solutions during electrocatalysis in acidic solution as the solution can etch away Sr atoms. We experimentally show this with porous SrTiO3-SrIrO3 solid-solution nanotubes synthesized by a facile synthetic route that contain 56 % less iridium than IrO2 yet show an order of magnitude higher apparent catalytic activity for OER in acidic solution. 相似文献
93.
Lifen Wang Lei Liu Ji Chen Ali Mohsin Jung Hwan Yum Todd W. Hudnall Christopher W. Bielawski Tijana Rajh Xuedong Bai Shang-Peng Gao Gong Gu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(36):15864-15870
Using high-resolution transmission electron microscopy and electron energy-loss spectroscopy, we show that beryllium oxide crystallizes in the planar hexagonal structure in a graphene liquid cell by a wet-chemistry approach. These liquid cells can feature van-der-Waals pressures up to 1 GPa, producing a miniaturized high-pressure container for the crystallization in solution. The thickness of as-received crystals is beyond the thermodynamic ultra-thin limit above which the wurtzite phase is energetically more favorable according to the theoretical prediction. The crystallization of the planar phase is ascribed to the near-free-standing condition afforded by the graphene surface. Our calculations show that the energy barrier of the phase transition is responsible for the observed thickness beyond the previously predicted limit. These findings open a new door for exploring aqueous-solution approaches of more metal-oxide semiconductors with exotic phase structures and properties in graphene-encapsulated confined cells. 相似文献
94.
Dr. Haoxuan Li Haifei Wen Dr. Zhijun Zhang Dr. Nan Song Prof. Ryan T. K. Kwok Prof. Jacky W. Y. Lam Prof. Lei Wang Prof. Dong Wang Prof. Ben Zhong Tang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20551-20555
Using reverse thinking of the aggregation-induced emission (AIE) principle, we demonstrate an ingenious and universal protocol for amplifying molecular motions to boost photothermal efficiency of fibers. Core–shell nanofibers having the olive oil solution of AIE-active molecules as the core surrounded by PVDF-HFP shell were constructed by coaxial electrospinning. The molecularly dissolved state of AIE-active molecules allows them to freely rotate and/or vibrate in nanofibers upon photoexcitation and thus significantly elevates the proportion of non-radiative energy dissipation, affording impressive heat-generating efficiency. Photothermal evaluation shows that the core–shell nanofibers with excellent durability can reach up to 22.36 % of photothermal conversion efficiency, which is 26-fold as the non-core–shell counterpart. Such a core–shell fiber can be used for photothermal textiles and solar steam generation induced by natural sunlight with green and carbon-zero emission. 相似文献
95.
Meng Lv Yang Yu María E. Sandoval-Salinas Prof. Jianhua Xu Dr. Zuhai Lei Prof. David Casanova Prof. Youjun Yang Prof. Jinquan Chen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(49):22363-22368
Spiro conjugation has been proposed to dictate the efficiency of charge transfer, which could directly affect the spin–orbit charge transfer intersystem crossing (SOCT-ISC) process. However, this process has yet to be exemplified. Herein, we prepared three spirobis[anthracene]diones, in which two benzophenone moieties are locked in close proximity and differentially functionalized to fine-tune the charge transfer state. Its feasibility for SOCT-ISC was theoretically predicted, then experimentally evaluated. Through fine-tuning the spiro conjugation coupling and varying the solvent dielectric constants, ISC rate constants were engineered to vary in a dynamic range of three orders of magnitude, from 7.8×108 s−1 to 1.0×1011 s−1, which is the highest ISC rate reported for SOCT-ISC system to our knowledge. Our findings substantiate the key factors for effective SOCT-ISC and offer a new avenue for the rational design of heavy atom free triplet sensitizers. 相似文献
96.
Lei Wang Kenan Zhang Yuzhuo Wang Wenbo Li Mingjie Chen Prof. Dr. Junliang Zhang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(11):4451-4457
Reported here is a highly efficient Pd/Xiang-Phos catalyzed enantioselective carboetherification of alkenyl oximes with either aryl or alkenyl halides, delivering various chiral 3,5-disubstituted and 3,5,5-trisubstituted isoxazolines in good yields with up to 97 % ee. The sterically bulky and electron-rich (S,Rs)- NMe-X2 ligand is responsible for the excellent reactivities and enantioselectivities. The salient features of this transformation include mild reaction conditions, general substrate scope, good functional-group tolerance, good yields, high enantioselectivities, easy scale-up, and application in the late-stage modification of bioactive compounds. The obtained products can be readily transformed into useful chiral 1,3-aminoalcohols. 相似文献
97.
Yiliang Wang Liu-Pan Yang Xiang Zhao Lei Cui Jian Li Xueshun Jia Jianhui Fang Chunju Li 《Molecules (Basel, Switzerland)》2020,25(24)
Conformational exchanges of synthetic macrocyclic acceptors are rather fast, which is rarely studied in the absence of guests. Here, we report multiple stimuli-responsive conformational exchanges between two preexisting conformations of 2,2′,4,4′-tetramethoxyl biphen[3]arene (MeBP3) macrocycle. Structures of these two conformations are both observed in solid state, and characterized by 1H NMR, 13C NMR and 2D NMR in solution. In particular, conformational exchanges can respond to solvents, temperatures, guest binding and acid/base addition. The current system may have a role to play in the construction of molecular switches and other stimuli-responsive systems. 相似文献
98.
Lei Liu Wes Lee Mingbin Yuan Chris Acha Michael B. Geherty Brandon Williams Osvaldo Gutierrez 《Chemical science》2020,11(12):3146
Design and implementation of the first (asymmetric) Fe-catalyzed intra- and intermolecular difunctionalization of vinyl cyclopropanes (VCPs) with alkyl halides and aryl Grignard reagents has been realized via a mechanistically driven approach. Mechanistic studies support the diffusion of alkyl radical intermediates out of the solvent cage to participate in an intra- or intermolecular radical cascade with a range of VCPs followed by re-entering the Fe radical cross-coupling cycle to undergo (stereo)selective C(sp2)–C(sp3) bond formation. This work provides a proof-of-concept of the use of vinyl cyclopropanes as synthetically useful 1,5-synthons in Fe-catalyzed conjunctive cross-couplings with alkyl halides and aryl/vinyl Grignard reagents. Overall, we provide new design principles for Fe-mediated radical processes and underscore the potential of using combined computations and experiments to accelerate the development of challenging transformations.Design and implementation of the first (asymmetric) Fe-catalyzed intra- and intermolecular difunctionalization of vinyl cyclopropanes (VCPs) with alkyl halides and aryl Grignard reagents has been realized via a mechanistically driven approach. 相似文献
99.
Xianhao Lv Mizhen Sun Lei Xu Runzhe Wang Huayi Zhou Yuyu Pan Shitong Zhang Qikun Sun Shanfeng Xue Wenjun Yang 《Chemical science》2020,11(19):5058
Designing a donor–acceptor (D–A) molecule with a hybridized local and charge transfer (HLCT) excited state is a very effective strategy for producing an organic light-emitting diode (OLED) with a high exciton utilization efficiency and external quantum efficiency. Herein, a novel twisting D–π–A fluorescent molecule (triphenylamine–anthracene–phenanthroimidazole; TPAAnPI) is designed and synthesized. The excited state properties of the TPAAnPI investigated through photophysical experiments and density functional theory (DFT) analysis reveal that its fluorescence is due to the HLCT excited state. The optimized non-doped blue OLED using TPAAnPI as a light-emitting layer exhibits a novel blue emission with an electroluminescence (EL) peak at 470 nm, corresponding to the Commission International de L''Eclairage (CIE) coordinates of (0.15, 0.22). A fabricated device termed Device II exhibits a maximum current efficiency of 18.09 cd A−1, power efficiency of 12.35 lm W−1, luminescence of ≈29 900 cd cm−2, and external quantum efficiency (EQE) of 11.47%, corresponding to a high exciton utilization efficiency of 91%. Its EQE remains as high as 9.70% at a luminescence of 1000 cd m−2 with a low efficiency roll-off of 15%. These results are among the best for HLCT blue-emitting materials involved in non-doped blue fluorescent OLEDs. The performance of Device II highlights a great industrial application potential for the TPAAnPI molecule.A new pure fluorescent blue HLCT-emitter was designed and synthesized. Highly efficient non-doped blue OLEDs with low efficiency roll-off were achieved. 相似文献
100.
Huan Li Lei Guo Xiaoliang Feng Liping Huo Shengqing Zhu Lingling Chu 《Chemical science》2020,11(19):4904
A selective, sequential C–O decarboxylative vinylation/C–H arylation of cyclic alcohol derivatives enabled by visible-light photoredox/nickel dual catalysis is described. This protocol utilizes a multicomponent radical cascade process, i.e. decarboxylative vinylation/1,5-HAT/aryl cross-coupling, to achieve efficient, site-selective dual-functionalization of saturated cyclic hydrocarbons in one single operation. This synergistic protocol provides straightforward access to sp3-enriched scaffolds and an alternative retrosynthetic disconnection to diversely functionalized saturated ring systems from the simple starting materials.A selective, sequential C–O decarboxylative vinylation/C–H arylation of cyclic alcohol derivatives enabled by visible-light photoredox/nickel dual catalysis has been described. 相似文献