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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.
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
3.
4.
The field of medicinal inorganic chemistry is rapidly advancing. In particular organometallic complexes have much potential as therapeutic and diagnostic agents. The carbon‐bound and other ligands allow the thermodynamic and kinetic reactivity of the metal ion to be controlled and also provide a scaffold for functionalization. The establishment of structure–activity relationships and elucidation of the speciation of complexes under conditions relevant to drug testing and formulation are crucial for the further development of promising medicinal applications of organometallic complexes. Specific examples involving the design of ruthenium and osmium arene complexes as anticancer agents are discussed. 相似文献
5.
In this study, a genetically encoded bioluminescent indicator for ERK2 dimer was developed with the split Renilla luciferase complementation method, in which the formation of ERK2 dimer induces a spontaneous emission of bioluminescence in living cells. In response to extracellular stimuli, such as epidermal growth factor (EGF) or 17β‐estradiol (E2), extracellular signal‐regulated kinase 2 (ERK2) is phosphorylated by its upstream kinase MEK, and also phosphorylates its substrates in various regions of the cell, including the nucleus. Phosphorylated ERK2 is led to form its dimer, thereby transporting itself into the nucleus. We demonstrated with the indicator that stimulation with EGF or E2 induces the formation of ERK2 dimer in living MCF‐7 cells. The dynamics of this dimer formation was examined and discussed. 相似文献
6.
7.
Gallin Peter Prof. Dr. 《ZDM》2003,35(3):110-119
In order to emphasize functional thinking in mathematical education, arguments are brought forward for an early and frequent use of tree diagrams in teaching stochastics. Since set and tree diagrams can be regarded as two sides of the same matter, Bayes’ theorem, which is strongly associated with predicative set diagrams, need not be dealt with explicitly any longer. Set diagrams are replaced by tree diagrams that are labelled in detail and by tree inversion as a functional instrument of dealing with conditioned probabilities. This technique is demonstrated by three typical problems in the context of conditioned probability. Finally, two letters by Pascal to Fermat are analysed in order to illustrate that predicative and functional approaches were already pursued in the early stages of probability calculus in the 17th century. 相似文献
8.
Ryosuke Sakai Issei Otsuka Toshifumi Satoh Ryohei Kakuchi Harumi Kaga Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):325-334
The asymmetric polymerization of 4′‐isocyanatobenzo‐18‐crown‐6 with the lithium amide of (S)‐(2‐methoxymethyl)pyrrolidine successfully proceeded to afford end‐functionalized poly(4′‐isocyanatobenzo‐18‐crown‐6) with (S)‐(2‐methoxymethyl)pyrrolidine (polymer 2 ). In the circular dichroism (CD) spectrum of 2 , a clear positive Cotton effect was observed in the range of 240–350 nm corresponding to the absorption of the polymer backbone, indicating that 2 partially formed a one‐handed helical structure, which was preserved by the chirality of (S)‐(2‐methoxymethyl)pyrrolidine bonding to the terminal end in 2 . In the titration experiments for the CD intensity of 2 in the presence of D ‐ and L ‐Phe·HClO4 (where Phe is phenylalanine), a small but remarkable difference was observed in the amount of the chiral guest needed for saturation of the CD intensity and in the saturated CD intensity, indicating that the extremely stable, one‐handed helical part should exist in the main chain of 2 , which was not inverted even when the unfavorable chiral guest for the predominant helical sense, L ‐Phe·HClO4, was added. In addition, helical polymer 2 exhibited a chiral discrimination ability toward racemic guests; that is, the guests were extracted from the aqueous phase into the organic phase with enantiomeric excess. The driving force of the chiral discrimination ability of 2 should certainly be attributed to the one‐handed helical structure in 2 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 325–334, 2006 相似文献
9.
Yutaka Miura Toshifumi Satoh Atsushi Narumi Osamu Nishizawa Yoshio Okamoto Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(4):1436-1446
The copper‐mediated atom transfer radical polymerization of methyl methacrylate (MMA) in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) was studied to simultaneously control the molecular weight and tacticity. The polymerization using tris[2‐(dimethylamino)ethyl]amine (Me6TREN) as a ligand was performed even at ?78°C with a number‐average molecular weight (Mn) of 13,400 and a polydispersity (weight‐average molecular weight/number‐average molecular weight) of 1.31, although the measured Mn's were much higher than the theoretical ones. The addition of copper(II) bromide (CuBr2) apparently affected the early stage of the polymerization; that is, the polymerization could proceed in a controlled manner under the condition of [MMA]0/[methyl α‐bromoisobutyrate]0/[CuBr]0/[CuBr2]0/[Me6TREN]0 = 200/1/1/0.2/1.2 at ?20°C with an MMA/HFIP ratio of 1/4 (v/v). For the field desorption mass spectrum of CuIBr/Me6TREN in HFIP, there were [Cu(Me6TREN)Br]+ and [Cu(Me6TREN)OCH(CF3)2]+, indicating that HFIP should coordinate to the CuI/Me6TREN complex. The syndiotacticity of the obtained poly(methyl methacrylate)s increased with the decreasing polymerization temperature; the racemo content was 84% for ?78°C, 77% for ?30°C, 75% for ?20°C, and 63% for 30°C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1436–1446, 2006 相似文献
10.
Vladimir Rapić Prof. Dr. Karl Schlögl Brigitte Steinitz 《Monatshefte für Chemie / Chemical Monthly》1977,108(4):767-780
Starting from optically active methylferrocene-- and--carboxylic acids (1 a and1 b) of known absolute configuration and enantiomeric purity about 15 chiral ferrocenes (of each isomeric series— and ) were obtained by suitable ligand transformations. Thereby (almost) all possible chiral combinations of the ligands CH3, COOH (COO–), COOCH3, CN and NH2 (NH3
+) were accessible which are necessary for a potential test of approximations of chirality functions for compounds with basic symmetry C5v. The chiroptical properties of these disubstituted ferrocenes are recorded.Preliminary tests using a shortened Ansatz revealed large discrepancies between calculated () and found [M]D-values. Possible reasons for this failure are discussed.
61. Mitt. über Ferrocenderivate
39. Mitt.:A. Meyer, H. Neudeck undK. Schlögl, Chem. Ber.110, 1403 (1977).
60. Mitt.:V. Rapi, K. Schlögl undB. Steinitz, J. Organometal. Chem.94, 87 (1975). 相似文献
61. Mitt. über Ferrocenderivate
39. Mitt.:A. Meyer, H. Neudeck undK. Schlögl, Chem. Ber.110, 1403 (1977).
60. Mitt.:V. Rapi, K. Schlögl undB. Steinitz, J. Organometal. Chem.94, 87 (1975). 相似文献