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41.
Dr. Dai Wu Xiu-Fang Mo Prof. Piao He Dr. Hai-Ru Li Prof. Xiao-Yi Yi Prof. Chao Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(40):10313-10322
Seven three dimensional (3D) uranyl organic frameworks (UOFs), formulated as [NH4][(UO2)3(HTTDS)(H2O)] ( 1 ), [(UO2)4(HTTDS)2](HIM)6 ( 2 , IM=imidazole), [(UO2)4(TTDS)(H2O)2(Phen)2] ( 3 , Phen=1,10-phenanthroline), [Zn(H2O)4]0.5[(UO2)3(HTTDS)(H2O)4] ( 4 ), and {(UO2)2[Zn(H2O)3]2(TTDS)} ( 5 ), {Zn(UO2)2(H2O)(Dib)0.5(HDib)(HTTDS)} ( 6 , Dib=1,4-di(1H-imidazol-1-yl)benzene) and [Na]{(UO2)4[Cu3(u3-OH)(H2O)7](TTDS)2} ( 7 ) have been hydrothermally prepared using a rigid octadentate carboxylate ligand, tetrakis(3,5-dicarboxyphenyl)silicon(H8TTDS). These UOFs have different 3D self-assembled structures as a function of co-ligands, structure-directing agents and transition metals. The structure of 1 has an infinite ribbon formed by the UO7 pentagonal bipyramid bridged by carboxylate groups. With further introduction of auxiliary N-donor ligands, different structure of 2 and 3 are formed, in 2 the imidazole serves as space filler, while in 3 the Phen are bound to [UO2]2+ units as co-ligands. The second metal centers were introduced in the syntheses of 4–7 , and in all cases, they are part of the final structures, either as a counterion ( 4 ) or as a component of framework ( 5 − 7 ). Interesting, in 7 , a rare polyoxometalate [Cu3(μ3-OH)O7(O2CR)4] cluster was found in the structure. It acts as an inorganic building unit together with the dimer [(UO2)2(O2CR)4] unit. Those uranyl carboxylates were sufficiently determined by single crystal X-ray diffraction, and their topological structures and luminescence properties were analyzed in detail. 相似文献
42.
Dr. Yuwei Zhang Caiyun Zhang Prof. Yirong Mo Prof. Zexing Cao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(4):1402-1409
Designing and synthesizing a stable compound with a planar tetracoordinate silicon (ptSi) center is a challenging goal for chemists. Here, a series of potential aromatic ptSi compounds composed of four conjugated rings shared by a centrally embedded Si atom are theoretically designed and computationally verified. Both Born–Oppenheimer molecular dynamics (BOMD) simulations and potential energy surface scannings verify the high stability and likely existence of these compounds, particularly Si-16-5555 (SiN4C8H8) with 16 π electrons, under standard ambient temperature and pressure. Notably, the Hückel aromaticity rule, which works well for single rings, is inconsistent with the high stability of Si-16-5555 where the 16 p electrons are spread over four five-membered rings fused together. Bonding analyses show that the strong electron donation from the peripheral 12-membered conjugated ring with 16 π electrons to the vacant central atomic orbital Si 3pz leads to the stabilization for both the ptSi coordination and planar aromaticity. The partial occupation of Si 3pz results in the peculiar carbenoid-type behaviors for the amphoteric center. By modulating the electron density on the ring with substituent groups, we can regulate the nucleophilic and electrophilic properties of the central Si. 相似文献
43.
44.
Shengpeng Mo Xinya Zhao Shuangde Li Lili Huang Xin Zhao Quanming Ren Mingyuan Zhang Ruosi Peng Yanan Zhang Xiaobin Zhou Yinming Fan Prof. Qinglin Xie Prof. Yanbing Guo Prof. Daiqi Ye Prof. Yunfa Chen 《Angewandte Chemie (International ed. in English)》2023,62(50):e202313868
Solar-to-chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO2 reduction. Herein, a new concentrated solar-driven photothermal system coupling a dual-metal single-atom catalyst (DSAC) with adjacent Ni−N4 and Fe−N4 pair sites is designed for boosting gas-solid CO2 reduction with H2O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)−N−C DSAC exhibits a superior photothermal catalytic performance for CO2 reduction to CO (86.16 μmol g−1 h−1), CH4 (135.35 μmol g−1 h−1) and CH3OH (59.81 μmol g−1 h−1), which are equivalent to 1.70-fold, 1.27-fold and 1.23-fold higher than those of the Fe−N−C catalyst, respectively. Based on theoretical simulations, the Fermi level and d-band center of Fe atom is efficiently regulated in non-interacting Ni and Fe dual-atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)−N−C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni−N−N−Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO3 dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO3 pathways) for solar-driven photothermal CO2 reduction to initial CO production. 相似文献
45.
用从头算对丙烯和甲苯2个超共轭体系进行计算,结果表明甲基上氢原子参与超共轭时,其碳氢键键长增大,氢上集居数减少,丙烯、甲苯的甲基旋转势垒为7.61及0.096 kJ/mol.超共轭基作用相当于一带有孤对电子参与共轭之杂原子,超共轭体系不同构型稳定性可用M=sum from i=1 to 3(sinθ_i[sin(θ_i-α)+sinα])来表征。 相似文献
46.
Wanlong Xiao Yuhao Mo Jing Guo Zhishan Su Shunxi Dong Xiaoming Feng 《Chemical science》2021,12(8):2940
New types of C2-symmetric chiral macrodiolides are readily obtained via chiral N,N′-dioxide-scandium(iii) complex-promoted asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles. This protocol provides an array of enantioenriched macrodiolides with 16, 18 or 20-membered rings in moderate to good yields with high diastereoselectivities and excellent enantioselectivities through adjusting the length of the tether at the C3 position of indoles. Density functional theory calculations indicate that the formation of macrocycles is more favorable than that of 9-membered-ring lactones in terms of kinetics and thermodynamics. The potential utility of these intriguing chiral macrodiolide molecules is demonstrated in the enantiomeric recognition of aminols and chemical recognition of metal ions.An asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles was achieved by using a chiral N,N′-dioxide-scandium(iii) complex. 相似文献
47.
Mo YJ Jiang DL Uyemura M Aida T Kitagawa T 《Journal of the American Chemical Society》2005,127(28):10020-10027
A series of poly(aryl ether) dendrimer chloroiron(III) porphyrin complexes (LnTPP)Fe(III)Cl (number of aryl layers [n]=3 to 5) were synthesized, and their Boltzmann temperatures under IR irradiation were evaluated from ratios of Stokes to anti-Stokes intensities of resonance Raman bands. While the Boltzmann temperature of neat solvent was unaltered by IR irradiation (LnTPP)Fe(III)Cl (n=3 to 5), all showed a temperature rise that was larger than that of the solvent and greater as the dendrimer framework was larger. Among vibrational modes of the metalloporphyrin core, the temperature rise of an axial Fe-Cl stretching mode at 355 cm-1 was larger than that for a porphyrin in-plane mode at 390 cm-1. Although most of the IR energy is captured by the phenyl nu8 mode at 1597 cm-1 of the dendrimer framework, an anti-Stokes Raman band of the phenyl nu8 mode was not detected, suggesting the extremely fast vibrational relaxation of the phenyl mode. From these observations, it is proposed that the energy of IR photons captured by the aryl dendrimer framework is transferred to the axial Fe-Cl bond of the iron porphyrin core and then relaxed to the porphyrin macrocycle. 相似文献
48.
采用溶胶-沉积法合成了高选择性的Au/ZnO催化剂,用于1,3-丙二醇选择性氧化酯化为3-羟基丙酸甲酯的反应.研究了保护剂PVA用量、金溶胶合成温度、金负载量及催化剂循环利用对反应的影响,且优化了反应温度和反应压力,并对催化剂进行了XRD和TEM表征.结果表明,PVA∶Au(m/m)=1∶4、金溶胶合成温度25℃、金负载量1%的Au/ZnO对目标反应的催化活性最好,在100℃和Po2=2MPa的条件下1,3-丙二醇的转化率达82.8%,产物3-羟基丙酸甲酯的选择性达95.4%.Au纳米粒子的粒径影响催化性能,在Au平均粒径为2.8~6.1nm的范围内,产物选择性随Au纳米粒子的粒径的减小而增大,平均粒径在2.8~4.8nm的范围内时,催化剂具有较好的产物选择性(大于90%);Au/ZnO催化剂循环利用4次后催化性能(转化率和选择性)无明显下降;并推测了无碱条件下Au/ZnO选择性催化氧化1,3-丙二醇合成3-羟基丙酸甲酯的反应机制. 相似文献
49.
A simple, environmentally benign protocol for synthesis of hydrazones from carbonyl compounds and hydrazides has been developed in the presence of meglumine in aqueous-ethanol media at room temperature. The salient features of the present protocol are mild reaction conditions, short reaction time, high yields, operational simplicity, metal-free, applicability toward large-scale synthesis, and biodegradable and inexpensive catalyst. 相似文献
50.
A Multi‐Stimuli‐Responsive Oxazine Molecular Switch: A Strategy for the Design of Electrochromic Materials 下载免费PDF全文
Xiaojun Wang Chang Gu Hongzhi Zheng Dr. Yu‐Mo Zhang Prof. Sean Xiao‐An Zhang 《化学:亚洲杂志》2018,13(9):1206-1212
A multi‐state and multi‐stimuli‐responsive oxazine molecular switch that combines an electro‐base property and sensitive base/acid‐responsive properties was designed and synthesized. The multi‐state structures of the molecular switch, with different colors, were predicted by comparing the optical properties with reference molecules and confirmed by using NMR spectroscopy. The color‐switching mechanism under stimulation with acids and bases was investigated by using DFT calculations. Three single states can be obtained and the switching is unidirectional under acid and base stimulation. The electrochromic phenomenon of the molecular switch, which combines its electro‐base and base‐sensitive properties, was demonstrated. An electrochromic device that exhibited good electrochromic properties with excellent reversibility (2000 cycles) and high coloration efficiency (804 cm2 C?1) was successfully constructed. 相似文献