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61.
Eva Lucaccini Matteo Briganti Dr. Mauro Perfetti Dr. Laure Vendier Dr. Jean‐Pierre Costes Dr. Federico Totti Prof. Dr. Roberta Sessoli Prof. Dr. Lorenzo Sorace 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5552-5562
The magnetic behaviour of a Dy(LH)3 complex (LH? is the anion of 2‐hydroxy‐N′‐[(E)‐(2‐hydroxy‐3‐methoxyphenyl)methylidene]benzhydrazide) was analysed in depth from both theoretical and experimental points of view. Cantilever torque magnetometry indicated that the complex has Ising‐type anisotropy, and provided two possible directions for the easy axis of anisotropy due to the presence of two magnetically non‐equivalent molecules in the crystal. Ab initio calculations confirmed the strong Ising‐type anisotropy and disentangled the two possible orientations. The computed results obtained by using ab initio calculations were then used to rationalise the composite dynamic behaviour observed for both pure DyIII phase and YIII diluted phase, which showed two different relaxation channels in zero and non‐zero static magnetic fields. In particular, we showed that the relaxation behaviour at the higher temperature range can be correctly reproduced by using a master matrix approach, which suggests that Orbach relaxation is occurring through a second excited doublet. 相似文献
62.
63.
Emilio Ignesti Roberto Buffa Lorenzo Fini Emiliano Sali Marco V. Tognetti Stefano Cavalieri 《Optics Communications》2012,285(6):1185-1189
We present an experimental and theoretical investigation, performed on hot sodium atoms in a ladder scheme, showing the control of the absorption and of the propagation velocity of a probe light pulse with a spectral bandwidth as large as 1.8 GHz. The predictions of the theoretical model compare favorably with the experimental results. 相似文献
64.
65.
Marco Bellagamba Luigi Bencivenni Lorenzo Gontrani Leonardo Guidoni Claudia Sadun 《Structural chemistry》2013,24(3):933-943
In this work, we report a multitechnique (energy-dispersive X-ray diffraction, computational methods, and FTIR spectroscopy) study of the tautomeric equilibrium of 1,2,3-triazole, one of the few small nitrogen-containing eterocycles liquid at room temperature. The T-2H form (C 2v symmetry) is found to be strongly favored in gas and solid phases, whereas the neat liquid gives diffraction patterns that can be interpreted satisfactorily with the structure functions calculated from some molecular dynamics results for both T-2H and T-1H tautomers, although the T-2H form gives a slightly better agreement. 相似文献
66.
Aliphatic and aromatic amines are efficiently acylated by acetic, pivalic, benzoic, phthalic, or maleic anhydrides in ethyl acetate at room temperature. Under the same experimental conditions, amino alcohols are chemoselectively acylated at the amino group. 相似文献
67.
Martina Mazzoni Lorenzo Franco Alberta Ferrarini Carlo Corvaja Giovanni Zordan Gianfranco Scorrano 《Liquid crystals》2013,40(2):203-208
A nitroxide [60]fullerene adduct containing a pyrrolidine-1-oxyl group has been synthesized. Its orientational order in the nematic phase of the liquid crystal solvent 4,4′-azoxyanisole (PAA) has been measured from the variation of the EPR spectral parameters on passing from the isotropic to the nematic phase. Highly resolved EPR lines allow for precise evaluation of the shifts of the g, a N and a H values. Since the g and the hyperfine tensors are known, the order matrix could be obtained. This is compared with the one calculated with a theoretical model based on short range solute-solvent interactions, which predicts a considerable degree of orientation of the molecular axes, despite the almost spherical shape of the molecule. The agreement with experimental findings is quite good and it is further improved if a bent structure of the pyrrolidine ring is taken into account. 相似文献
68.
Dr. Samir Safi Dr. Gaëlle Creff Dr. Aurélie Jeanson Lei Qi Christian Basset Dr. Jérome Roques Dr. Pier Lorenzo Solari Prof. Eric Simoni Dr. Claude Vidaud Prof. Christophe Den Auwer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(34):11261-11269
Herein, we describe the structural investigation of one possible uranyl binding site inside a nonstructured protein. This approach couples spectroscopy, thermodynamics, and theoretical calculations (DFT) and studies the interaction of uranyl ions with a phosphopeptide, thus mimicking a possible osteopontin (OPN) hydroxyapatite growth‐inhibition site. Although thermodynamical aspects were investigated by using time‐resolved laser fluorescence spectroscopy (TRLFS) and isothermal titration calorimetry (ITC), structural characterization was performed by extended X‐ray absorption fine structure (EXAFS) at the U LIII‐edge combined with attenuated total reflection Fourier transform infrared (ATR‐FTIR) spectroscopy. From the vibrational and fluorescence spectra, several structural models of a UO22+/peptide complex were developed and subsequently refined by using theoretical calculations to fit the experimental EXAFS obtained. The structural effect of the pH value was also considered under acidic to moderately acidic conditions (pH 1.5–5.5). Most importantly, the uranyl/peptide coordination environment was similar to that of the native protein. 相似文献
69.
Dr. Mónica Arrate Dr. Aritz Durana Dr. Paula Lorenzo Prof. Dr. Ángel R. de Lera Prof. Dr. Rosana Álvarez Dr. José M. Aurrecoechea 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(41):13893-13900
Carbonyl‐tethered propargylic benzoates undergo intramolecular carbonylpropargylation upon treatment with Et2Zn in the presence of a catalytic amount of Pd0 with the formation of 2‐alkynylcyclopentanol products. A ligand/solvent effect on the cis/trans selectivity (referring to the relative positions of alkynyl and OH groups) of ring‐closure has been found. In a non‐coordinating solvent (benzene), increasing the electron‐donating ability of the phosphine ligand (while decreasing its dissociation ability) leads to an increased tendency towards the trans product. On the other hand, the combination of a coordinating solvent (THF) and PPh3, an easily dissociated phosphine, results in the exclusive formation of cis products. Experimental and computational results are compatible with a divergent behavior of an allenylethylpalladium intermediate that partitions between competitive carbonyl‐addition and transmetalation pathways, each leading to a different diastereoisomer. These results also suggest that the dissociating ability of the phosphine regulates that behavior. 相似文献
70.
Pablo Fuentealba Lorenzo Serón Camila Sánchez Jorge Manzur Verónica Paredes-Garcia Nancy Pizarro 《Journal of Coordination Chemistry》2014,67(23-24):3894-3908
A family of macrocyclic complexes [M2LnCl2] have been synthesized and characterized (M: CuII or ZnII; Ln: macrocyclic ligand derived from 2-hydroxy-5-methyl-1,3-benzenedicarbaldehyde and different aliphatic diamines and o-phenylenediamine). The influence of the aromaticity of the ligand and the metal center on the spectroscopic properties of the complexes (absorption and emission) has been studied. Making use of the weak interactions between hydrated potassium ions and the layers of the K0.4Mn0.8PS3 precursor, the obtained macrocyclic complexes have been intercalated in the interlamellar space by a microwave assisted cationic exchange reaction. The optical properties of the obtained hybrid materials are reported. The absorption edge, recorded by solid state reflectance spectroscopy for CuII and the ZnII macrocycle-based composites, is 1.67–1.76 eV, both shifted to lower energy compared with that of the pristine MnPS3. 相似文献