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931.
Alberola A Carter E Constantinides CP Eisler DJ Murphy DM Rawson JM 《Chemical communications (Cambridge, England)》2011,47(9):2532-2534
The β-sheet structure associated with chlorinated aromatics (d(Cl···Cl)≈ 4.0 ?) has been implemented to drive formation of π-stacked structures of dithiadiazolyl radicals. Both title compounds exhibit an increase in paramagnetism above 150 K but solid-state EPR studies indicate that the origin of the paramagnetism in these two systems is different. 相似文献
932.
Barceló-Oliver M Estarellas C Terrón À García-Raso Á Frontera A 《Chemical communications (Cambridge, England)》2011,47(16):4646-4648
We have recently communicated the resemblance of 1-hexyluracil in the crystal state with a lipid bilayer (CrystEngComm, 2010, 12, 362-365). Treatment of this molecule with silver nitrate yields a model, using a non-essential metal ion, of a uracil quartet with geometric parameters comparable to those previously found in RNA strands. 相似文献
933.
Raducan M Rodríguez-Escrich C Cambeiro XC Escudero-Adán EC Pericàs MA Echavarren AM 《Chemical communications (Cambridge, England)》2011,47(17):4893-4895
[Au(tmbn)(2)](SbF(6)) is the first gold(I) complex supported by two nitrile ligands that is indefinitely stable at room temperature. This is a highly versatile precatalyst that can be used for the preparation of active and robust solid-supported gold(I) catalysts. 相似文献
934.
Machado AE Gomes WR Araújo DM Miglio HS Ueno LT De Paula R Cavaleiro JA Barbosa Neto NM 《Molecules (Basel, Switzerland)》2011,16(7):5807-5821
An imidazolium tetrasubstituted cationic porphyrin derivative (the free base and its Zn(II) complex) with five-membered heterocyclic groups in the meso-positions were synthesized using microwave irradiation, and the compounds obtained characterized by (1)H-NMR and mass spectrometry. We observed that under microwave irradiation the yield is similar to when the synthesis is performed under conventional heating, however, the time required to prepare the porphyrins decreases enormously. In order to investigate the electronic state of these compounds, we employed UV-Vis and fluorescence spectroscopy combined with quantum chemical calculations. The results reveal the presence, in both compounds, of a large number of electronic states involving the association between the Soret and a blue-shifted band. The Soret band in both compounds also shows a considerable solvent dependence. As for emission, these compounds present low quantum yield at room temperature and no solvent influence on the fluorescence spectra was observed. 相似文献
935.
Fillipe V. Rocha Carolina V. Barra Silmar J. S. Franchi Adelino V. G. Netto Antonio E. Mauro Regina C. G. Frem 《Journal of Thermal Analysis and Calorimetry》2011,106(2):385-389
Four new mononuclear Pd(II) complexes of the type [PdX2(tdmPz)] {X = Cl− (1); Br− (2); I− (3); SCN− (4); tdmPz = 1-thiocarbamoyl-3,5-dimethylpyrazole} have been synthesized and characterized by elemental analysis, IR spectroscopy,
1H and 13C{1H}-NMR experiments. The thermal behavior of the complexes 1–4 has been investigated by means of thermogravimetry (TG) and differential thermal analysis (DTA). From the initial decomposition
temperatures, the thermal stability of the complexes can be ordered in the sequence: 3 < 4 ≡ 2 < 1. The final products of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction. 相似文献
936.
Jos�� M. L��pez-de-Luzuriaga Miguel Monge M. Elena Olmos Mar��a Rodr��guez-Castillo Antonio Laguna Fernando Mendizabal 《Theoretical chemistry accounts》2011,129(3-5):593-602
The interaction of bisperhalophenyl aurates [AuR2]? (R?=?C6F5, C6F3Cl2, and C6Cl5) with the closed-shell Ag+, Cu+, and Tl+ ions has been studied theoretically and compared with the experimentally known X-ray diffraction crystal structures. Initially, the aurates have been fully optimized at MP2 level of theory in a D 2h symmetry. The analysis of the basicity of the three aurates [AuR2]? (R?=?C6F5, C6F3Cl2 and C6Cl5) against Ag+ ions in a C 2v symmetry has been calculated in point-by-point bsse-corrected interaction energy analysis at HF and MP2 levels of theory. Taking into account the experimental observation of additional interactions between the heterometals and C ipso atoms at the perhalophenyl rings or halogen atoms at the ortho position of the perhalophenyl rings, dinuclear models of the type [AuR2]?···Ag+ (R?=?C6Cl5, and C6F5); [AuR2]?···Cu+ (R?=?C6F5, and C6Cl5) and [AuR2]?···Tl+ (R?=?C6F5, and C6Cl5) with a C 2v , C 2 , and C s symmetries have been optimized at DFT-B3LYP level. The interaction energies have been computed through bsse-corrected single point HF and MP2 calculations. The energy stabilization provided and the heterometal preference have been analyzed and compared with the experimental results. 相似文献
937.
Radovan Bast Kenneth Ruud Antonio Rizzo Trygve Helgaker 《Theoretical chemistry accounts》2011,129(3-5):685-699
We present the first relativistic study of the electric-field-gradient induced birefringence (Buckingham birefringence), with application to the series of molecules CX2 (X?=?O, S, Se, Te). A recently developed atomic-orbital-driven scheme for the calculation of time-dependent molecular properties using one-, two- and four-component relativistic wave functions (Bast et?al. in Chem Phys 356:177, 2009) is extended to first-order frequency-dependent magnetic-field perturbations, using London atomic orbitals to ensure gauge-origin independent results and to improve basis-set convergence. Calculations are presented at the Hartree?CFock and Kohn?CSham levels of theory and results for CO2 and CS2 are compared with previous high-level coupled-cluster calculations. Except for the heaviest member of the series, relativistic effects are small??in particular for the temperature-independent contribution to the birefringence. By contrast, the effects of electron correlation are significant. However, the reliability of standard exchange-correlation functionals in describing Buckingham birefringence remains unclear based on the comparison with high-level coupled-cluster singles-and-doubles calculations. 相似文献
938.
939.
Luis A. Toledo-Matos Maximo Antonio Pech-Canul 《Journal of Solid State Electrochemistry》2011,15(9):1927-1934
The evolution under open-circuit conditions of iron passive films formed at 0.8 VSCE in a borate buffer solution at pH 8.4 was investigated with electrochemical impedance spectroscopy (EIS) and cyclic voltammetry.
The composition of the freshly formed passive film as determined by X-ray photoelectron spectroscopy (XPS) was found to be
in agreement with a bilayer model, where the inner layer is composed mainly of iron oxide and the outer layer consists of
a hydrated material. Results of XPS measurements also showed that the open-circuit breakdown of passive films was consistent
with a reductive dissolution mechanism. When the iron electrode reached an intermediate stage in the open-circuit potential
decay (approximately −0.3 VSCE), the oxide film, containing both Fe(II) and Fe(III), was still protective. The impedance response in this stage exhibited
a mixed control by charge transfer at the metal/film and film/solution interfaces and diffusion of point defects through the
film. At the final stage of the open-circuit potential decay (approximately −0.7 VSCE), the oxide film was very thin, and the ratio of Fe3+/Fe2+ and O2−/OH− had decreased significantly. The impedance response also exhibited a mixed charge-transfer–diffusion control, but the diffusion
process was related to transport of species in the electrolyte solution resulting from dissolution of the oxide film. 相似文献
940.
Jaime-Vasconcelos MÁ Frontana-Uribe BA Morales-Serna JA Salmón M Cárdenas J 《Molecules (Basel, Switzerland)》2011,16(11):9109-9115
From the aerial parts of Salvia occidentalis (Labiatae) a new diterpenoid with a rearranged neo-clerodane skeleton was isolated. This new compound was named salvioccidentalin and its structure was established by spectroscopic means. A probable biogenetic relationship with salvigenolide from S. fulgens and salvileucalin A and spiroleucantholide from Salvia leucantha is proposed. 相似文献