Effects of substituents on bridging ligands on the single‐molecule magnet properties of Zn2Dy2 cluster complexes

Two new Zn₂Dy₂ complexes were constructed from Zn (II) salen‐type Schiff base complex fragment and 2,6‐pyridinedimethanol (H₂pdm) or its Br‐substituted analogue (4‐bromopyridine‐2,6‐diyl)dimethanol (H₂Brpdm); their molecular formulas are [Zn₂Dy₂(L)₂(pdm)₂(MeOH)₂](ClO₄)₂ [ 1 , H₂L = N, N′‐ bis(3‐methoxysalicylidene)‐1,3‐diaminopropane] and [Zn₂Dy₂(L)₂(Brpdm)₂(MeOH)₂](ClO₄)₂ [ 2 ], the Dy (III) ions of which have a NO₇ triangular dodecahedral coordination sphere. The two complexes show not only ferromagnetic interaction but also field‐induced single‐molecule magnet (SMM) behavior, which are rare Dy (III)‐containing cluster complexes with the NO₇ triangular dodecahedral coordination sphere that can show good magnetic relaxation. The energy barrier value of complex 2 is higher than those of complex 1 and the Dy (III) complexes with the DyNO₇ triangular dodecahedral coordination configuration reported in the literature.     

一类压缩型映射的不动点定理

在完备的度量空间中,讨论了一类新型的非线性压缩映射ρ(Tx,Ty)≤a(ρ(x,y))ρ(x,Tx)+b(ρ(x,y))ρ(y,Ty)+c(ρ(x,y))ρ(x,y)通过构造迭代序列,指出该映射的不动点的存在性和唯一性,并给出相应的误差估计式,拓展和改进了有关文献的范围.     

Portable single-sided NMR measurements at variable temperatures: Implementation of a thermo-controlled device and application to the heating of bread dough

A temperature control unit was implemented to vary the temperature of samples studied on a commercial Mobile Universal Surface Explorer nuclear magnetic resonance (MOUSE-NMR) apparatus. The device was miniaturized to fit the maximum MOUSE sampling depth (25 mm). It was constituted by a sample holder sandwiched between two heat exchangers placed below and above the sample. Air was chosen as the fluid to control the temperature at the bottom of the sample, at the interface between the NMR probe and the sample holder, in order to gain space. The upper surface of the sample was regulated by the circulation of water inside a second heat exchanger placed above the sample holder. The feasibility of using such a device was demonstrated first on pure water and then on several samples of bread dough with different water contents. For this, T1 relaxation times were measured at various temperatures and depths and were then compared with those acquired with a conventional compact closed-magnet spectrometer. Discussion of results was based on biochemical transformations in bread dough (starch gelatinization and gluten heat denaturation). It was demonstrated that, within a certain water level range, and because of the low magnetic field strength of the MOUSE, a linear relationship could be established between T1 relaxation times and the local temperature in the dough sample.     

Microstructure and dielectric study of pure BST and doped BSTF ceramic materials by broadband dielectric spectroscopy

Pure BST and doped BSTF (with BSTF2: Fe₂O₃ 2 wt % and BSTF4: Fe₂O₃ 4 wt %) ceramics were prepared by solid state reaction. XRD pattern showed the different phases were formed depend on the weight percent of Fe₂O₃. The crystal size and lattice parameters increased while the lattice strain decreased. The topography of the sintered samples shows increase of the grain size with increasing Fe₂O₃ ratio and hence enhances the compaction of ceramics. Broadband dielectric spectroscopy was employed to investigate the effect of magnetite nanoparticle on the dielectric properties of the pure BST ceramic. The interfacial polarization and the conductivity contribution reflect the high values of permittivity and its gradual increase as frequency decreases. The two BSTF samples show relaxation peak dynamic originated from presence of immobile species/electrons at low temperatures and defects/vacancies results from the formation of oxygen vacancies originates from the spontaneous change in oxidation states of Fe ions (Fe ^3+/Fe²⁺) at high temperatures. The relaxation rate obeys Arrhenius law at high temperatures in case of BST sample with activation energy 225 kJ/mol. This high value of activation energy at higher temperatures reflects and confirms the slowed down of the dynamics at the interphase and the decoupling nature of the OH-dynamic and the interfacial polarization.     

Molecular dynamic study of dielectric polarization and ferroelectricity in a model polar polymer

Molecular dynamics simulations are used to explore the polarization response of a lamellar crystal consisting of folded chains of a highly simplified model polar polymer. The system is based on a united atom model of polyethylene with constrained bond lengths and bond angles, and it is endowed with artificial partial charges placed on the united atoms to give it a simple polar character. Simulations performed with various temperatures, electric field directions, and electric field application histories reveal a complicated sequence of reorientation processes, including pronounced ferroelectric behavior. The sequence includes a weak, temperature‐independent prompt response, and a slow‐rising delay regime with stretched exponential behavior and thermally‐activated reorientation parameters consistent with trans‐gauche (TG) barrier crossings in the amorphous phase. When the delay regime has progressed sufficiently, a primary large‐amplitude response due to organized rotation of large subsegments in the crystalline phase occurs in a rapid manner that requires relatively few TG barrier crossings. A final, extremely slow rise in residual polarization completes the sequence. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 740–759     

Evaluation of alumina slurry dispersion by nuclear magnetic resonance relaxation as a comparison to conventional dispersion evaluation methods

In this paper, we evaluated the particle dispersion degree of alumina slurry containing a dispersant by solvent nuclear magnetic resonance (NMR) relaxation and compared it with conventional dispersion evaluation methods such as viscosity, particle size, and sedimentation height measurements. The dispersion of slurry was evaluated via numerical analysis of the transverse relaxation time (T₂). The effect of the changes in different parameters of the experiment in terms of milling time, solid loading, and dispersant amount was investigated by NMR relaxation as well as conventional methods. The results of NMR relaxation measurements revealed that T₂ correlates well with other dispersion evaluation methods; thus, it is an efficient technique to evaluate the dispersion of alumina slurry, specifically, when studying the effect of the change in milling time and dispersion amount.     

Macroscopic and microscopic electrical properties of a ferrofluid in a low frequency field

Using the complex dielectric permittivity measurements, in the frequency range 20 Hz – 2 MHz and at temperatures between (25–70) ^∘C, the polarizability (α), the electric modulus (M) and the electrical conductivity (σ), of a ferrofluid sample, were determined. The results enabled the computation of the thermal activation energy of electrical conduction, the obtained value being approximately equal, at 0.15 eV. By eliminating the losses arising from electrical conduction, we highlighted the existence of a Schwarz type dielectric relaxation, in the sample, at the frequency above 5 kHz. These results allowed, for the first time, the evaluation of the mechanical mobility, u, of the ions on the particle surface, resulting in a value of, $u=3.4\cdot {10}^8$ m/s N. Knowledge of macroscopic and microscopic electrical properties is useful in explaining the dielectric polarization mechanisms and relaxation processes of ferrofluids, and also in the use of ferrofluids in technological and biomedical applications.     

Excited State Dynamics of Isolated 6- and 8-Hydroxyquinoline Molecules

The photoinduced dynamics of isolated n-hydroxyquinoline (nHQ) molecules (n=6,8) was investigated in femtosecond pump-probe experiments. A qualitative difference was found between 8HQ and 6HQ. After an initial rapid decay corresponding to the departure of the initial wavepacket out of the Franck-Condon region of the excitation, the 8HQ probe signal decays to zero in 0.37 ps whereas a much longer time constant of 10.4 ps is observed in 6HQ. This interrogates on the role played by the intramolecular H-bond N HO which is at play the 8HQ molecule. Ab-initio were performed at the MCSCF/aug-cc-pVDZ level on the 8HQ molecule to help the discussion. A complex energy landscape was found, which includes a conical intersection.     

Solvent Effects in the Homogeneous Catalytic Reduction of Propionaldehyde with Aluminium Isopropoxide Catalyst: New Insights from PFG NMR and NMR Relaxation Studies

Solvent effects in homogeneous catalysis are known to affect catalytic activity. Whilst these effects are often described using qualitative features, such as Kamlet-Taft parameters, experimental tools able to quantify and reveal in more depth such effects have remained unexplored. In this work, PFG NMR diffusion and T₁ relaxation measurements have been carried out to probe solvent effects in the homogeneous catalytic reduction of propionaldehyde to 1-propanol in the presence of aluminium isopropoxide catalyst. Using data on diffusion coefficients it was possible to estimate trends in aggregation of different solvents. The results show that solvents with a high hydrogen-bond accepting ability, such as ethers, tend to form larger aggregates, which slow down the molecular dynamics of aldehyde molecules, as also suggested by T₁ measurements, and preventing their access to the catalytic sites, which results in the observed decrease of catalytic activity. Conversely, weakly interacting solvents, such as alkanes, do not lead to the formation of such aggregates, hence allowing easy access of the aldehyde molecules to the catalytic sites, resulting in higher catalytic activity. The work reported here is a clear example on how combining traditional catalyst screening in homogeneous catalysis with NMR diffusion and relaxation time measurements can lead to new physico-chemical insights into such systems by providing data able to quantify aggregation phenomena and molecular dynamics.     

A new formulation for fictitious mass of viscous dynamic relaxation method

Abstract

In this article, a new relationship is proposed for the fictitious mass of viscous dynamic relaxation (DR) method. First, incremental equations are derived for DR steps. Using transformed Gershgörin theory, a new relationship is achieved for fictitious mass of viscous DR by formulating modified time step ratio. This procedure presents a new algorithm for the viscous DR method. To evaluate the numerical efficiency of the proposed method, some 2D and 3D truss and frame structures are analyzed with elastic linear and geometrically nonlinear behaviors. Results show that by using the proposed algorithm for fictitious mass, the convergence rate of the viscous DR method is improved so that the proposed algorithm presents the structural response with lower iterations in comparison with other common DR techniques.

Communicated by Joerg Fehr.