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71.
Chunhong Wang Qi Cui Zhixin Zhang Prof. Zhu-Jun Yao Dr. Shaozhong Wang Prof. Zhi-Xiang Yu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(42):9821-9826
1,3-Azaprotio transfer of propargylic α-ketocarboxylate oximes, a new type of alkynyl oximes featuring an ester tether, has been explored by taking advantage of gold catalysis. The incorporation of an oxygen atom to the chain of alkynyl oximes led to the formation of two different oxa-cyclic nitrones. It was found that internal alkynyl oximes with an E-configuration deliver five-membered nitrones, whereas terminal alkynyl oximes with an E-configuration afford six-membered nitrones. DFT calculations on four possible pathways supported a stepwise formation of C−N and C−H bonds, in which a 1,3-acyloxy-migration competes with the 1,3-azaprotio-transfer, especially in the case of internal alkynyl oximes. The relative nucleophilic properties of oxygen in the carbonyl group and the nitrogen in the oxime, the electronic effects of alkynes, and the influence of the ring system have been investigated computationally. 相似文献
72.
Vera Deneva 《Molecular physics》2019,117(13):1613-1620
ABSTRACTThe tautomeric optical sensors based on 4-(phenyldiazenyl)naphthalen-1-ol exist in their pure enol tautomeric form as free ligands, while the addition of metal ion fully shifts the equilibrium towards the keto tautomer allowing a red shift in the measured absorbance. This effect is achieved when a side ionophore group is connected to a tautomeric backbone by a spacer in a way that stabilizes the enol form via hydrogen boding. When the ionophore captures the metal ion the keto form is stabilized due to C─O tautomeric group participation in the complex. In the current study, we model theoretically the effect of symmetric tweezer like ionophores (RCOXCOR, where X, being CH or N, is the linker to the tautomeric backbone) on the tautomeric state and complexation ability of 4-(phenyldiazenyl)naphthalen-1-ol containing ligands. It was found that enol form stabilisation is achieved when R?=?NMe2, independing on the linker. Both ligands are unsuitable for capturing alkali metal ions. The calculations predict that the complexation with alkali earth metal ions could lead to a full shift of the tautomeric equilibrium towards keto tautomer. 相似文献
73.
New carbohydrazone ligand derived from the condensation of carbohydrazide and ethyl acetoacetate, diethyl 3,3′‐(carbonylbis (hydrazin‐2‐yl‐1‐ylidene))(3E,3′E)‐dibutyrate (H4EBC), and its divalent Co, Ni and Cu chelates have been isolated and characterized utilizing convenient methods. 1H‐NMR spectrum of H4EBC revealed the abundance of the enol isomer in solution, which was the opposite to what was shown by the solid IR. This was supported by comparing the theoretical IR of both keto and enol forms. In [Ni(H4EBC)Cl2(H2O)]·2H2O, H4EBC acts as a neutral NON tridentate ligand via the (C=O)carbonyl oxygen atom besides the two (C=N)azomethine nitrogen atoms, while in [Co(H4EBC)Cl2(2H2O)]·2H2O, H4EBC behaves as a neutral NN bidentate ligand through the two azomethine groups. Magnetic measurements inherent to their electronic spectra show that both Ni (II) and Co (II) chelates have octahedron coordination frameworks. On the other hand, the ligand behaves as a binegative tetradentate in [Cu2(H4EBC)Cl2]·H2O via the deprotonated (C=O)carbonyl groups of the ethyl acetoacetate framework and the two (C=N)azomethine groups. In the latter complex, the carbonyl group of the carbohydrazide moiety is converted to hydroxyl group. Cu (II) complex has a tetrahedral geometry according to ESR and electronic spectral data. The reaction of H4EBC with SmCl3·6H2O or LnCl3·7H2O gave single crystals of abnormal product (C16H16N4O4). The packing diagram of this crystal has a chain structure. The photoluminescence spectra of [Cu 2 (H 4 EBC)Cl 2 ]·H 2 O , [Co(H 4 EBC)Cl 2 (H 2 O) 2 ]·2H 2 O and [Ni(H 4 EBC)Cl 2 (H 2 O)]·2H 2 O display emission broad‐bands at 342, 321 and 337 nm, respectively. The microbial behavior of the synthesized moieties was investigated against various bacterial and fungal strains. [Cu2(H4EBC)Cl2]·H2O complex shows the same activity as ampicillin towards Escherichia coli and Staphylococcus aureus with inhibition zones of 26 and 22 mm, respectively. Antioxidant activity is determined using bleomycin‐dependent DNA damage assay besides erythrocyte hemolysis. Finally, in vitro cytotoxic activities against two different cell lines have been examined. 相似文献
74.
For seeking high‐efficiency narrow‐band‐gap donor materials to enhance short‐circuit current density for organic solar cells, a series of oligo‐selenophene (OS) and oligo(3,4‐ethylenedioxyselenophene) (OEDOS) with various chain lengths were designed and characterized using density functional theory (DFT) and time‐dependent DFT calculations. Based on the results, it can be seen that with increasing chain length of the oligomers in both syn‐ and anti‐adding manners, the bond length alternation is decreased which indicates that the π‐electron delocalization is increased. Also, when the chain length is increased the electronic energy gap and the optical energy gap are decreased. It can be concluded that the syn‐(OS)n=10,14,15, anti‐(OS)n=14 and anti‐(OEDOS)n=7–12 oligomers can act as low‐band‐gap polymers. Therefore they can absorb more sunlight based on maximum wavelength (higher than 620 nm). Furthermore, a red shift in the simulated absorption spectra of (OS)n and (OEDOS)n donors is observed. It is found that (OS)n=14,15 with syn configuration of the extended oligomers is the most suitable donor for the design of high‐performance organic solar cells possessing a narrow electronic band gap, high exciton lifetime and broad and intense absorption spectra that cover the solar spectrum leading to complete light‐harvesting efficiency. 相似文献
75.
Two LnIII ions are sandwiched by dinuclear CoII building blocks derived from a tris‐triazamacrocyclic ligand bearing pendant carboxylic acid functionality, 1,3,5‐tris((4,7‐bis(2‐carboxyethyl)‐1,4,7‐triazacyclonon‐1‐yl)methyl)‐benzene (H6L), giving rising to two nanoscale heterometallic metal–organic cages formulated as [Co4Ln2(LH2.5)2(H2O)4]·(ClO4)6·NO3·nH2O [Ln = Dy, n = 12 ( 1 ); Ln = Yb, n = 9 ( 2 )], whose internal cavity accommodates a guest NO3? anion. Their hexanuclear cage‐like architectures are maintained both in solution and solid states as confirmed by mass spectrum as well as X‐ray diffraction experiments. These two cages display ligand‐based fluorescence emissions and therefore both were chosen to be operated as fluorescent chemosensors for the detection of nitroaromatic compounds. Attractively, these metal–organic cages allow highly selective and sensitive detection of picric acid (PA) over other nitroaromatics in solution and suspension, and the fluorescence resonance energy transfer (FRET) between the cage probes and PA is mainly responsible for the remarkable detection efficiency. 相似文献
76.
A series of dinuclear cycloplatinated(II) complexes with general closed formula of [Pt2Me2(C^N)2(μ‐P^P)] (C^N = 2‐vinylpyridine (Vpy), 2,2′‐bipyridine N‐oxide (O‐bpy), 2‐(2,4‐difluorophenyl)pyridine (dfppy); P^P = 1,1‐bis(diphenylphosphino)methane (dppm), N,N‐bis(diphenylphosphino)amine (dppa)) are reported. The complexes were characterized by means of NMR spectroscopy. Due to the presence of dppm and dppa with short backbones as bridging ligands, two platinum centres are located in front of each other in these complexes so a Pt…Pt interaction is established. Because of this Pt…Pt interaction, the complexes have bright orange colour under ambient light and are able to strongly emit red light under UV light exposure. These strong red emissions originate from a 3MMLCT (metal–metal‐to‐ligand charge transfer) electronic transition. In most of these complexes, the emissions have unstructured bell‐shaped bands, confirming the presence of large amount of 3MMLCT character in the emissive state. Only the complexes bearing dfppy and dppa ligands reveal dual luminescence: a high‐energy structured emission originating from 3ILCT/3MLCT (intra‐ligand charge transfer/metal‐to‐ligand charge transfer) and an unstructured low‐energy band associated with 3MMLCT. In order to describe the nature of the electronic transitions, density functional theory calculations were performed for all the complexes. 相似文献
77.
Chikashi Shinagawa Yusuke Morikawa Shin-ichi Nishimura Hiroshi Ushiyama Atsuo Yamada Koichi Yamashita 《Journal of computational chemistry》2019,40(1):237-246
Na2FePO4F is a promising cathode material for a Na-ion battery because of its high electronic capacity and good cycle performance. In this work, first principle calculations combined with cluster expansion and the Monte Carlo method have been applied to analyze the charge and discharge processes of Na2FePO4F by examining the voltage curve and the phase diagram. As a result of the density functional theory calculation and experimental verification with structural analysis, we found that the most stable structure of Na1.5FePO4F has the P21/b11 space group, which has not been reported to date. The estimated voltage curve has two clear plateaus caused by the two-phase structure composed of P21/b11 Na1.5FePO4F and Pbcn Na2FePO4F or Na1FePO4F and separated along the c-axis direction. The phase diagram shows the stability of the phase-separated structure. Considering that Na2FePO4F has diffusion paths in the a- and c-axis directions, Na2FePO4F has both innerphase and interphase diffusion paths. We suggest that the stable two-phase structure and the diffusion paths to both the innerphase and interphases are a key for the very clear plateau. We challenge to simulate a nonequilibrium state at high rate discharge with high temperature by introducing a coordinate-dependent chemical potential. The simulation shows agreement with the experimental discharge curve on the disappearance of the two plateaus. © 2018 Wiley Periodicals, Inc. 相似文献
78.
79.
Seema Yadav Sriparna Ray Ajeet Singh Shaikh M. Mobin Tapta Kanchan Roy Chandrakanta Dash 《应用有机金属化学》2020,34(11):e5942
Dinuclear gold(I)-N-heterocyclic carbene complexes were developed for the hydrohydrazidation of terminal alkynes. The gold(I)-N-heterocyclic carbene complexes 2a-2b were synthesized in good yields from silver complexes synthesized in situ, which in turn were obtained from the corresponding imidazolium salts with Ag2O in dichloromethane as a solvent. The new air-stable gold(I)-NHC complexes, 2a - 2b, were characterized using NMR spectroscopy, elemental analysis, infrared, and mass spectroscopy studies. The gold(I) complex 2a was characterized using X-ray crystallography. Bis-N-heterocyclic carbene–based gold(I) complexes 2a - 2b exhibited excellent catalytic activities for hydrohydrazidation of terminal alkynes yielding acylhydrazone derivatives. The working catalytic system can be used in gram-scale synthesis. In addition, the catalytic reaction mechanism of the hydrohydrazidation of terminal alkynes by gold(I)-NHC complex was studied in detail using density functional theory. 相似文献
80.
An integrated shape morphing and topology optimization approach based on the deformable simplicial complex methodology is developed to address Stokes and Navier‐Stokes flow problems. The optimized geometry is interpreted by a set of piecewise linear curves embedded in a well‐formed triangular mesh, resulting in a physically well‐defined interface between fluid and impermeable regions. The shape evolution is realized by deforming the curves while maintaining a high‐quality mesh through adaption of the mesh near the structural boundary, rather than performing global remeshing. Topological changes are allowed through hole merging or splitting of islands. The finite element discretization used provides smooth and stable optimized boundaries for simple energy dissipation objectives. However, for more advanced problems, boundary oscillations are observed due to conflicts between the objective function and the minimum length scale imposed by the meshing algorithm. A surface regularization scheme is introduced to circumvent this issue, which is specifically tailored for the deformable simplicial complex approach. In contrast to other filter‐based regularization techniques, the scheme does not introduce additional control variables, and at the same time, it is based on a rigorous sensitivity analysis. Several numerical examples are presented to demonstrate the applicability of the approach. 相似文献