排序方式: 共有77条查询结果,搜索用时 15 毫秒
1.
Dr. Jessica Flores Gonzalez Vincent Montigaud Dr. Vincent Dorcet Dr. Kevin Bernot Dr. Boris Le Guennic Dr. Fabrice Pointillart Prof. Olivier Cador 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(39):10160-10168
Single-Molecule Magnet (SMM) property is by essence molecular, while commonly measured in solid crystalline state. Solvent crystallization molecules are usually neglected in the analysis and interpretation of solid-state properties. The solvation/desolvation process in the polyoxometalate(POM)-based Na9[Er(W5O18)2] ⋅ 35 H2O SMM demonstrates that the dehydrated form relaxes more than 1000 times faster than the initial state, while the rehydration process allows the quasi complete recovering of the initial magnetic behaviour. This dehydration process is monitored by thermogravimetric analysis (TGA) and temperature-dependent X-ray powder diffraction, and rationalized by periodic quantum chemical calculations evidencing the tremendous role of the labile water molecules in the stability of the edifice. Ab-initio calculations highlight that sodium ions localization in the structure drive the magnetic responses. Isotopic enrichment with nuclear spin free (166Er, I=0) ErIII ions shows that the relaxation dynamics in the quantum regime depends on the nuclear spin. 相似文献
2.
Pramila Selvanathan Gang Huang Thierry Guizouarn Dr. Thierry Roisnel Dr. Guglielmo Fernandez‐Garcia Dr. Federico Totti Dr. Boris Le Guennic Dr. Guillaume Calvez Dr. Kévin Bernot Dr. Lucie Norel Prof. Stéphane Rigaut 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(43):15222-15226
A spiropyran‐based switchable ligand isomerizes upon reaction with lanthanide(III) precursors to generate complexes with an unusual N3O5 coordination sphere. The air‐stable dysprosium(III) complex shows a hysteresis loop at 2 K and a very strong axial magnetic anisotropy generated by the merocyanine phenolate donor. 相似文献
3.
Unraveling the Crystal Structure of Lanthanide–Murexide Complexes: Use of an Ancient Complexometry Indicator as a Near‐Infrared‐Emitting Single‐Ion Magnet 下载免费PDF全文
Xiaohui Yi Dr. Kevin Bernot Vincent Le Corre Dr. Guillaume Calvez Dr. Fabrice Pointillart Dr. Olivier Cador Dr. Boris Le Guennic Julie Jung Dr. Olivier Maury Dr. Virginie Placide Dr. Yannick Guyot Dr. Thierry Roisnel Dr. Carole Daiguebonne Prof. Olivier Guillou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(6):1569-1576
Herein, we provide some structural evidence of the complexation color‐change of murexide solutions in presence of lanthanide, which has been used for decades in complexometric studies. For Ln=Sm to Lu and Y, the compounds crystallize as monomeric [Ln(Murex)3] ? 11 H2O with an N3O6 tricapped square‐antiprism environment, which are stable up to 250 °C. Single‐ion magnet (SIM) behavior is then observed on the YbIII derivative in an original nine‐coordinated environment. In‐field slow relaxation (Δ=(15.6±1) K; τ0=2.73×10?6 s) is observed with a very narrow distribution of the relaxation time (αmax=0.09). Magnetic and photophysical properties can be correlated. On one hand the analysis of NIR emission spectrum permits to have access to crystal field parameters and to compare them with those extracted from dc measurements. On the other hand, magnetic measurements permit to identify the nature of the M J states involved in the 2F5/2→2F7/2 luminescence spectrum. The gap between the low‐lying states is in agreement with the energy barrier obtained from magnetic slow‐relaxation measurement. 相似文献
4.
Dr. Siddhartha De Dr. Alexandrine Flambard Dr. Delphine Garnier Patrick Herson Dr. Frank H. Köhler Dr. Abhishake Mondal Dr. Karine Costuas Dr. Béatrice Gillon Prof. Rodrigue Lescouëzec Dr. Boris Le Guennic Dr. Frédéric Gendron 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(52):12120-12136
The local magnetic structure in the [FeIII(Tp)(CN)3]− building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutron diffraction (PND) with first-principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin-density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanido ligands: Spin-polarization on the carbon atoms and spin-delocalization on the nitrogen atoms. The results of our combined density functional theory (DFT) and multireference calculations were found in good agreement with the PND results and the experimental NMR chemical shifts. Moreover, the ab-initio calculations allowed us to connect the experimental spin-density map characterized by PND and the suggested distribution of the spin-density on the ligands observed by NMR spectroscopy. Interestingly, significant differences were observed between the pseudo-contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using a simple point-dipole model. These discrepancies underline the limitation of the point-dipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contact and pseudo-contact contributions. 相似文献
5.
Le Guennic B Kirchner B Reiher M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(24):7448-7460
In several recent studies Schrock and collaborators demonstrated for the first time how molecular dinitrogen can be catalytically transformed under mild and ambient conditions to ammonia by a molybdenum triamidoamine complex. In this work, we investigate the geometrical and electronic structures involved in this process of dinitrogen activation with quantum chemical methods. Density functional theory (DFT) has been employed to calculate the coordination energies of ammonia and dinitrogen relevant for the dissociation/association step in which ammonia is substituted by dinitrogen. In the DFT calculations the triamidoamine chelate ligand has been modeled by a systematic hierarchy of increasingly complex substituents at the amide nitrogen atoms. The most complex ligand considered is an experimentally known ligand with an HMT = 3,5-(2,4,6-Me3C6H2)2C6H3 substituent. Several assumptions by Schrock and collaborators on key reaction steps are confirmed by our calculations. Additional information is provided on many species not yet observed experimentally. Particular attention is paid to the role of the charge of the complexes. The investigation demonstrates that dinitrogen coordination is enhanced for the negatively charged metal fragment, that is, coordination is more favorable for the anionic metal fragment than for the neutral species. Coordination of N2 is least favorable for the cationic metal fragment. Furthermore, ammonia abstraction from the cationic complex is energetically unfavorable, while NH3 abstraction is less difficult from the neutral and easily feasible from the anionic low-spin complex. 相似文献
6.
Le Guennic B Neugebauer J Reiher M Autschbach J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1677-1686
The experimental 13C NMR chemical shift of the central carbon atom in the octahedral [(Ph3PAu)6C]2+ cluster was investigated on the basis of relativistic density functional calculations. In order to arrive at independent model conclusions regarding the value of the chemical shift, a systematic study of the dependence of the cluster structure on the phosphine ligands, the chosen density functionals, and the basis set size was conducted. The best structures obtained were then used in the NMR calculations. Because of the cage-like cluster structure a pronounced deshielding of the central carbon nucleus could have been expected. However, upon comparison with the 13C NMR properties of the related complex [C{Au[P(C6H5)2(p-C6H4NMe2)]}6]2+, Schmidbaur et al. have assigned a signal at delta=135.2 ppm to the interstitial carbon atom. Our calculations confirm this value in the region of the aromatic carbon atoms of the triphenylphosphine ligands. The close-lying signals of the 108 phenyl carbon atoms can explain the difficulties of assigning them experimentally. 相似文献
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8.
Bourdolle A Allali M Mulatier JC Le Guennic B Zwier JM Baldeck PL Bünzli JC Andraud C Lamarque L Maury O 《Inorganic chemistry》2011,50(11):4987-4999
Two europium complexes with bis(bipyridine) azamacrocyclic ligands featuring pendant arms with or without π-conjugated donor groups are synthesized and fully characterized by theoretical calculations and NMR spectroscopy. Their photophysical properties, including two-photon absorption, are investigated in water and in various organic solvents. The nonfunctionalized ligand gives highly water-stable europium complexes featuring bright luminescence properties but poor two-photon absorption cross sections. On the other hand, the europium complex with an extended conjugated antenna ligand presents a two-photon absorption cross section of 45 GM at 720 nm but is poorly luminescent in water. A detailed solvent-dependent photophysical study indicates that this luminescence quenching is not due to the direct coordination of O-H vibrators to the metal center but to the increase of nonradiative processes in a protic solvent induced by an internal isomerization equilibrium. 相似文献
9.
Vérot M Rota JB Kepenekian M Le Guennic B Robert V 《Physical chemistry chemical physics : PCCP》2011,13(14):6657-6661
The chemical control of magnetic and conduction properties for organic radicals is mainly based on t, the resonance integral, and U, the on-site repulsion, used in the Hubbard model. A qualitative analysis based on the competition between the kinetic and the Coulomb contribution, and the expression of the magnetic exchange coupling suggests that U should be roughly 800 cm(-1) while the resonance integral |t| should be 200 cm(-1) to reach bifunctionality. Ab initio wavefunction-based calculations allowed us to quantitatively measure those quantities for several organic materials considered as 1D systems starting from their reported crystal structures. The extraction of t and U parameters from the exchange coupling constants between neighbouring radicals allowed us to anticipate a possible metallic behaviour. Finally, the impact of chemical changes in the constitutive units is measured to rationalize the macroscopic behaviour modifications. It is shown that the intriguing regime characterized by simultaneous itinerant and localized electrons might be achieved by molecular engineering. 相似文献
10.
L. Znaidi G.J.A.A. Soler Illia R. Le Guennic C. Sanchez A. Kanaev 《Journal of Sol-Gel Science and Technology》2003,26(1-3):817-821
Microcrystalline ZnO films presenting well-defined and tunable orientation were obtained by spin coating of alcoholic sols by two different approaches, based on controlled hydrolysis-condensation of Zn-ethanolamine complexes. As-deposited films are formed by amorphous zinc oxide-acetate submicronic particles, which are transformed into oriented ZnO after thermal treatment. The orientation of ZnO depends on the synthesis method, and the solvent. While in ethanol and [Zn] = 0.05 mol·L–1, films consist of rectangular platelets oriented with the (100) planes parallel to the substrate (a//n), the orientation of the particles changes to (c//n) for systems in 2-methoxyethanol (2-ME) and [Zn] = 0.75 mol·L–1. A study of chemical factors that influence the orientation (precursor, solvent, MEA/Zn ratio, concentration, coating parameters, heat treatment) is presented. 相似文献