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1.
Giang Truong Nguyen Prof. Dr. Liviu Ungur 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(30):e202200227
Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs. 相似文献
2.
Dr. Konrad Natterer 《Monatshefte für Chemie / Chemical Monthly》1885,6(1):519-522
Ohne Zusammenfassung 相似文献
3.
Akira Yanagisawa Prof. Dr. Takahiro Suzuki Takanori Koide Shogo Okitsu Takayoshi Arai Prof. Dr. 《化学:亚洲杂志》2008,3(10):1793-1800
A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13. 相似文献
4.
Silica@copper (SiO2@Cu) core–shell nanoparticles were synthesized and well characterized by XRD, TEM, AFM, XPS, UV/Vis, TGA–MS, and ICP–AES techniques. The synthesized SiO2@Cu core–shell nanoparticles were employed as catalysts for the conjugate addition of amines to α,β‐unsaturated compounds in water to obtain β‐amino carbonyl compounds in excellent yields in shorter reaction times. Furthermore, the catalyst works well for hetero‐Michael addition reactions of heteroatom nucleophiles such as thiols to α,β‐unsaturated compounds. As the reaction is performed in water, it allows for easy recycling of the catalyst with consistent activity. 相似文献
5.
6.
D. Citterio Stefan Rásonyi Ursula E. Spichiger 《Fresenius' Journal of Analytical Chemistry》1996,354(7-8):836-840
New chromoionophores have been developed, focused on NIR applications so that optode membranes may be used in monolithically integrated optical sensors. The wavelength of maximum absorbance has been estimated for a new model compound by the Pariser-Parr-Pople (PPP) method. Several cyanine type dyes have been tested as membrane chromoionophores. Membrane composition has been altered to overcome solubility problems. In this way, simple pH-sensitive optode membranes have been produced. 相似文献
7.
Kristin Fischer Silvio Prause Stefan Spange Frank Cichos Christian Von Borczyskowski 《Journal of Polymer Science.Polymer Physics》2003,41(11):1210-1218
Solvent‐dependent ultraviolet–visible (UV–vis) absorption and Stokes shifts including strong hydrogen‐bond‐donating (HBD) solvents such as 2,2,2‐trifluoroethanol and 1,1,1,3,3,3‐hexafluoro‐2‐propanol of two coumarine dyes (Co 151 and Co 153) were analyzed with multiple‐square analyses of linear solvation energy relationships and the Kamlet–Taft solvent parameter set to α (HBD capacity), β (hydrogen‐bond‐accepting capacity), and π* (dipolarity/polarizability). The UV–vis absorption and emission spectra of Co 151 and Co 153 were measured when adsorbed on various polysaccharides such as different cellulose batches, carboxymethylcelluloses with different degrees of substitution, and chitine. As a result of this evaluation, Co 153 is recommended as an alternative UV–vis probe for evaluating the dipolarity/polarizability of cellulose and cellulose derivates. Multiple adsorption of Co 153 on Linters cellulose took place indicating a wide‐surface polarity distribution, which makes the determination of a rigid polarity parameter questionable. Thus, fluorescence measurements of adsorbed Co 153 are suitable to detect inhomogenities on a surface but not for the determination of empirical polarity parameters. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1210–1218, 2003 相似文献
8.
Mingyang Zhao Warren T. Ford Stefan H. J. Idziak Nicholas C. Maliszewskyj Paul A. Heiney 《Liquid crystals》1994,16(4):583-599
The hexa-4-dodecyloxybenzoyl derivative 1 of azacrown [18]-N6 was originally reported to have a 'tubular' mesophase on the basis of its large central ring and 6-fold symmetry. Starting in the mesophase, annealing of 1 under a cover slip results in formation of a new crystalline phase that melts directly to an isotropic liquid at the temperature previously observed for the mesophase to isotropic transition. Thus the phase behaviour of 1 is kinetically controlled. The analogous hexa-3,4-bisdodecyloxybenzoyl derivative 2 of azacrown [18]-N6 has no kinetic limitations to its phase changes and has an enantiotropic columnar liquid crystalline phase. We have synthesized side chain copolysiloxanes with a (CH2)11 spacer and 75-84 per cent by weight of the same 4-dodecyloxybenzoyl-[18]-N6 mesogen. The polysiloxanes also display a liquid crystalline phase. 相似文献
9.
S. Scott Collis Kaveh Ghayour Matthias Heinkenschloss Michael Ulbrich Stefan Ulbrich 《国际流体数值方法杂志》2002,40(11):1401-1429
The control of complex, unsteady flows is a pacing technology for advances in fluid mechanics. Recently, optimal control theory has become popular as a means of predicting best case controls that can guide the design of practical flow control systems. However, most of the prior work in this area has focused on incompressible flow which precludes many of the important physical flow phenomena that must be controlled in practice including the coupling of fluid dynamics, acoustics, and heat transfer. This paper presents the formulation and numerical solution of a class of optimal boundary control problems governed by the unsteady two‐dimensional compressible Navier–Stokes equations. Fundamental issues including the choice of the control space and the associated regularization term in the objective function, as well as issues in the gradient computation via the adjoint equation method are discussed. Numerical results are presented for a model problem consisting of two counter‐rotating viscous vortices above an infinite wall which, due to the self‐induced velocity field, propagate downward and interact with the wall. The wall boundary control is the temporal and spatial distribution of wall‐normal velocity. Optimal controls for objective functions that target kinetic energy, heat transfer, and wall shear stress are presented along with the influence of control regularization for each case. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
10.
The shock structure problem is one of the classical problems of fluid mechanics and at least for non-reacting dilute gases it has been considered essentially solved. Here we present a few recent findings, to show that this is not the case. There are still new physical effects to be discovered provided that the numerical technique is general enough to not rule them out a priori. While the results have been obtained for dense fluids, some of the effects might also be observable for shocks in dilute gases. 相似文献