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11.
第一过渡系中的顺磁性离子CrⅢ、MnⅡ/MnⅢ、FeⅡ/FeⅢ、CoⅡ、NiⅡ和CuⅡ及抗磁性离子CoⅢ和ZnⅡ均可与DyⅢ在多齿螯合配体配位下形成单分子磁体配合物。在本文中,我们阐述或汇总了几乎所有的第一过渡系金属-镝单分子磁体。对于由顺磁性第一过渡金属离子和DyⅢ离子形成的配合物,有2个有趣的现象需要引起人们的注意:一是一些Cr-Dy配合物具有较高的阻塞温度和较大的矫顽场,这可归功于配合物内CrⅢ离子和DyⅢ离子之间较强的磁耦合作用(|J|>10 cm-1)。二是报道的FeⅡ2-Dy配合物的能垒可达到319 cm-1(459 K),这在第一过渡系金属-镝单分子磁体中也是比较高的。这可能与FeⅡ2-Dy中DyⅢ具有较高的轴向对称性(D5h)有关,且从头计算表明该配合物中Dy的第一激发态也具有较高的轴向对称性。除了部分Cr-Dy和FeⅡ-Dy配合物外,其他顺磁性第一过渡金属-Dy的能垒较低,这可能由配合物内顺磁离子间弱的磁耦合造成的。为了消除磁耦合对磁弛豫行为影响,近年来人们关注于使用抗磁性第一过渡金属离子与DyⅢ构建单分子磁体配合物。相比其他核数的Zn-Dy配合物,三核Zn2Dy配合物被报道的数目最多且研究得最为深入,这可能与较易调控Zn2Dy中Dy配位几何对称性有关。最后,我们提出了几点关于进一步提升第一过渡系金属-镝单分子磁体的磁性能的建议,其中最为重要的是控制Dy配位几何的轴向对称性及Dy的基态mJ的电荷分布。对于第一过渡系金属-镝单分子磁体中的DyⅢ离子,DyⅢ基态mJ的电荷与配体的电荷之间的静电排斥应该降到最低。 相似文献
12.
Kaori Kobayashi Takanori Matsui Shozo Tsunekawa 《Journal of Molecular Spectroscopy》2011,269(2):242-247
The trans-ethyl methyl ether molecule has three low-lying torsional modes, that is, two inequivalent methyl internal rotations and an asymmetric skeletal torsion. The internal rotations of the CCH3 and OCH3 methyl rotors and the skeletal torsion correspond to the vibrational modes, ν28, ν29 and ν30 respectively. In this study, the microwave absorption spectrum in the ν28 = 1 CCH3 torsional state was analyzed for the first time. Nine hundred fifty seven lines up to J = 48 and K = 4 were assigned, and the rotational, centrifugal distortion and internal rotational tunneling parameters were determined with the use of a tunneling matrix formalism. By combining the present results on the ν28 = 1 torsional state with those for the ν30 = 1 skeletal torsional state and the ν29 = 1 OCH3 torsional state, torsional couplings are estimated in order to understand quantitatively the inverted A/E sequence patterns observed for those three excited torsional states. 相似文献
13.
14.
Metal‐Catalyzed Reductive Coupling Reactions of Organic Halides with Carbonyl‐Type Compounds 下载免费PDF全文
Dr. Toni Moragas Dr. Arkaitz Correa Prof. Dr. Ruben Martin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(27):8242-8258
Metal‐catalyzed reductive coupling reactions of aryl halides and (pseudo)halides with carbonyl‐type compounds have undergone an impressive development within the last years. These methodologies have shown to be a powerful alternate strategy, practicality aside, to the use of stoichiometric, well‐defined, and, in some cases, air‐sensitive organometallic species. In this Minireview, the recent findings in this field are summarized, with particular emphasis on the mechanistic interpretation of the results and future aspects of this area of expertise. 相似文献
15.
Xanthine derivatives, caffeine (L1), theobromine (L2), theophylline (L3), 7-(β-hydroxyethyltheophylline) (L4), (7-(2,3-dihydroxypropyl)theophylline) (L5), and theophylline 7-acetic acid (L6) and the acetylated derivatives of the later three (L7–L9) were employed as ligands for the in situ palladium catalyzed Suzuki–Miyaura cross couplings of a series of halogenated pyridines. Optimized conditions were found where the diacetylated ligand (L8) was determined to be the best for this process, producing good to excellent yields in the couplings of halogenated anilines with phenylboronic acid under mild reaction conditions in water using microwave irradiation. 相似文献
16.
Xiaobing Xu 《Tetrahedron letters》2009,50(1):57-1346
A convenient one-pot synthesis of 1,4-benzoxazines via three-component coupling and subsequent O-cyclization is reported. The present reaction provides an efficient protocol to functionalized 1,4-benzoxazine derivatives in good to high yields from aldehydes, amines and alkynes. Furthermore, the O-annulation process is completely regio- and stereoselective, only the six-membered rings and its Z-isomers were obtained. 相似文献
17.
本文旨在研究具有相互作用的两个网络间的同步及其控制问题,从理论上我们证明了通过选择适当的控制项,两个网络可以达到同步.文中没有限制两个网络具有相同的动力学,针对两个网络的拓扑结构和网络问的作用矩阵,我们提出了两种自适应同步格式,最后通过数值算例来阐述我们得到的理论结果. 相似文献
18.
N. Thilagavathi A. Manimaran N. Padma Priya N. Sathya C. Jayabalakrishnan 《应用有机金属化学》2010,24(4):301-307
Four tridentate O, N, O donor Schiff base ligands were prepared by the reaction of substituted benzhydrazide and appropriate salicylaldehyde. The complexes of these ligands were synthesized by refluxing the ligands with ruthenium(II) starting complexes of the formula [RuHCl(CO)(EPh3)2B] in benzene, where E = P or As; B = PPh3 or AsPh3 or pyridine. The newly synthesized complexes were characterized by elemental, spectral (FT‐IR, UV and NMR) and electrochemical data. On the basis of the above studies, an octahedral structure has been proposed for all the complexes. The catalytic efficiency of the complexes in aryl–aryl couplings and oxidation of alcohols was examined and their inhibition activity against the growth of the micro‐organisms was also examined. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
19.
Monoalkylated acylguanidines are important functional groups in many biologically active compounds and additionally applied in coordination chemistry. Yet a straightforward assignment of the individual NH chemical shifts and the acylguanidine conformations is still missing. Therefore, in this study, NMR spectroscopic approaches for the chemical and especially the conformational assignment of protonated monoalkylated acylguanidines are presented. While NOESY and 3JH, H scalar couplings cannot be applied successfully for the assignment of acylguanidines, 4JH, H scalar couplings in 1H,1H COSY spectra allow for an unambiguous chemical shift and conformational assignment. It is shown that these 4JH, H long‐range couplings between individual acylguanidinium NH resonances are observed solely across all‐trans (w) pathways. Already one cis orientation in the magnetisation transfer pathway leads to signal intensities below the actual detection limit and significantly lower than cross‐peaks from 2JNH, NH couplings or chemical exchange. However, it should be noted that also in the case of conformational exchange being fast on the NMR time scale, averaged cross‐peaks from all‐trans 4JH, H scalar couplings are detected, which may lead at first glance to an incomplete or even wrong conformational analysis. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
20.
Perttu Permi Sami Heikkinen Ilkka Kilpelinen Arto Annila 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1999,139(2):273
1H-detected two-dimensional double-/zero-quantum experiments are described for measurement of homonuclear 2JHH-couplings of NH2 or CH2 groups in proteins. These experiments utilize multiple-quantum coherence for determination of the size and the absolute sign of the geminal scalar and dipolar couplings in the presence of broad lines. Spectra are simplified by gradient selection and spin-state selective filters. 相似文献