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2.
The nitridorhenium(V) complexes ReNCl(2)(PCy3)(2) (1), ReNBr(2)(PCy3)(2) (2), ReNCl(2)(PPh3)(2) (3), and ReNBr(2)(PPh3)(2) (4) produce structured emission spectra upon excitation at low temperature. The origin, E(00), occurs at 15 775, 16 375, 15 875, and 16 300 cm(-1), respectively. The vibronic peaks are regularly spaced with an average energy separation corresponding to the Re triple bond N stretching frequency. The nitridorhenium stretching frequency ranges from 1095 to 1101 cm(-1), as determined by Raman and IR spectroscopy. The excited-state distortions are calculated by fitting the emission spectra. The excited state arises primarily from a d(xy) (ReN nonbonding) to d(yz) (ReN pi antibonding) transition. The rhenium-nitrogen bond length in the excited state is 0.08 A longer than in the ground electronic state, which is consistent with the difference in bond lengths of ReN bonds of bond order 3 and bond order 2.5 as determined from molecular structures. 相似文献
3.
The dependence of Mentha pulegium L. (pennyroyal) essential oil composition, obtained by supercritical carbon dioxide (SC-CO2), with the following parameters: pressure, temperature, extraction time (dynamic), and modifier (methanol) was studied. The results were also compared with those obtained by conventional hydrodistillation method in laboratory conditions. Regarding the percentages of menthone (30.3%) and pulegone (52.0%), the optimum SFE results were obtained at the following experimental conditions: pressure=100 atm, T=35 °C, dynamic time=10 min, and Vmodifier=0 μl. The results of hydrodistillation showed that the major components of M. pulegium L. were pulegone (37.8%), menthone (20.3%), and piperitenone (6.8%). The evaluation of the composition of each extract was performed by gas chromatography-mass spectrometry. 相似文献
4.
Holliday JD Rodgers SL Willett P Chen MY Mahfouf M Lawson K Mullier G 《Journal of chemical information and computer sciences》2004,44(3):894-902
This paper evaluates the use of the fuzzy k-means clustering method for the clustering of files of 2D chemical structures. Simulated property prediction experiments with the Starlist file of logP values demonstrate that use of the fuzzy k-means method can, in some cases, yield results that are superior to those obtained with the conventional k-means method and with Ward's clustering method. Clustering of several small sets of agrochemical compounds demonstrate the ability of the fuzzy k-means method to highlight multicluster membership and to identify outlier compounds, although the former can be difficult to interpret in some cases. 相似文献
5.
Ison EA Trivedi ER Corbin RA Abu-Omar MM 《Journal of the American Chemical Society》2005,127(44):15374-15375
The rhenium oxo complex [Re(O)(hoz)2][TFPB], 1 (where hoz = 2-(2'-hydroxyphenyl)-2-oxazoline(-) and TFPB = tetrakis(pentafluorophenyl)borate) catalyzes the hydrosilation of aldehydes and ketones under ambient temperature and atmosphere. The major organic product is the protected alcohol as silyl ether. Isolated yields range from 86 to 57%. The reaction requires low catalyst loading (0.1 mol %) and proceeds smoothly in CH2Cl2 as well as neat without solvent. In the latter condition, the catalyst precipitates at the end of reaction, allowing easy separation and catalyst recycling. Re(O)(hoz)(H), 3, was prepared, and its involvement in an ionic hydrosilation mechanism was evaluated. Complex 3 was found to be less hydridic than Et3SiH, refuting its participation in catalysis. A viable mechanism that is consistent with experimental findings, rate measurements, and kinetic isotope effects (Et3SiH/Et3SiD = 1.3 and benzaldehyde-H/benzaldehyde-D = 1.0) is proposed. Organosilane is activated via eta2-coordination to rhenium, and the organic carbonyl adds across the coordinated Si-H bond [2 + 2] to afford the organic reduction product. 相似文献
6.
Structural Chemistry - In this work, the hydrogenation of acetylene on the Pd2/g-C3N4 catalyst is investigated by the density functional theory (DFT) and quantum theory of atoms in molecules... 相似文献
7.
Malekahmadi Omid Kalantar Mahdi Nouri-Khezrabad Mohsen 《Journal of Thermal Analysis and Calorimetry》2021,144(6):2109-2126
Journal of Thermal Analysis and Calorimetry - The hydroxyapatite is one of the biocompatible and insulating bioceramics, while the carbon nanotube has a high thermal conductivity potential. This... 相似文献
8.
Laura Parejo Dr. Mahdi Chaari Sara Santiago Dr. Gonzalo Guirado Prof. Francesc Teixidor Dr. Rosario Núñez Dr. Jordi Hernando 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(1):270-280
Icosahedral metallacarboranes are θ-shaped anionic molecules in which two icosahedra share one vertex that is a metal center. The most remarkable of these compounds is the anionic cobalt-based metallacarborane [Co(C2B9H11)2]−, whose oxidation-reduction processes occur via an outer sphere electron process. This, along with its low density negative charge, makes [Co(C2B9H11)2]− very appealing to participate in electron-transfer processes. In this work, [Co(C2B9H11)2]− is tethered to a perylenediimide dye to produce the first examples of switchable luminescent molecules and materials based on metallacarboranes. In particular, the electronic communication of [Co(C2B9H11)2]− with the appended chromophore unit in these compounds can be regulated upon application of redox stimuli, which allows the reversible modulation of the emitted fluorescence. As such, they behave as electrochemically-controlled fluorescent molecular switches in solution, which surpass the performance of previous systems based on conjugates of perylendiimides with ferrocene. Remarkably, they can form gels by treatment with appropriate mixtures of organic solvents, which result from the self-assembly of the cobaltabisdicarbollide-perylendiimide conjugates into 1D nanostructures. The interplay between dye π-stacking and metallacarborane electronic and steric interactions ultimately governs the supramolecular arrangement in these materials, which for one of the compounds prepared allows preserving the luminescent behavior in the gel state. 相似文献
9.
The linear 3D piezoelasticity theory in conjunction with the versatile transfer matrix approach and the wave equation for the internal acoustic domain are employed for active non-stationary vibroacoustic response control of an arbitrarily thick, tri-laminate, fluid-filled, simply supported, piezocomposite cylindrical tank, excited by arbitrary (non-axisymmetric) time-dependent on-surface mechanical loads. The smart structure is composed of a supporting core layer of functionally graded orthotropic material perfectly bonded to inner and outer spatially distributed radially polarized functionally graded piezoceramic sensor and uniform force actuator (FGPM) layers. Active vibration damping is implemented by transferring the accumulated voltage on the sensor layer to the piezoelectric actuator layer in context of proportional and derivative control laws. Durbin's numerical inverse Laplace transform scheme is utilized to calculate the time response histories of the relevant interface displacement/stress components, center-point acoustic pressure, and actuator voltage, for selected loading configurations (i.e., concentrated step, impulse, and moving external loads). Numerical simulations demonstrate the effectiveness of the adopted distributed sensing/actuation configuration together with the active damping control strategy in suppressing the vibroacoustic response of a three-layered (Ba2NaNb5O15/Al/PZT4) water-filled piezoelastic cylindrical tank. Limiting cases are considered and the validity of results is established by comparison with the available data as well as with the aid of a commercial finite element package. 相似文献
10.
A facile, one-pot synthesis of new phenanthridine derivatives by a three-component reaction between phenantridine, dialkyl acetylenedicarboxylates(DAADs), and aromatic aldehydes is described. The reaction is characterized by mild conditions, high selectivity, and tolerance to various functional groups. 相似文献