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21.
Rikkou M Manos M Tolis E Sigalas MP Kabanos TA Keramidas AD 《Inorganic chemistry》2003,42(15):4640-4649
Reaction of the non-oxo V(IV) species [V(IV)Cl(2)(L(OO))(2)] [L(OO) = acetylacetonate (acac(-)) or benzoylacetonate (bzac(-))] with a chelate nitrogen-donor ligand L(NN) in acetonitrile leads to the reduction of V(IV) to V(III) and the formation of the mononuclear V(III) compounds of the general formula [V(III)Cl(2)(L(OO))(L(NN))] (L(OO) and L(NN) are acac(-) and bipy for 1; acac- and 5,5'-me(2)bipy for 2; acac(-) and 4,4'-tb(2)bipy for 3; acac(-) and phen for 4; bzac(-) and bipy for 5; bzac(-) and phen for 6). The reduction of the V(IV) complexes was monitored by GC-MS and (1)H NMR spectroscopy. Both one- and two-dimensional (2D COSY and 2D EXSY) (1)H NMR techniques were used to assign the observed (1)H NMR resonances of 1-6 in CD(2)Cl(2) or CDCl(3) solution. It appeared that in solution these V(III) complexes form two isomers which are in equilibrium: cis-[V(III)Cl(2)(L(OO))(L(NN))] <==> trans-[V(III)Cl(2)(L(OO))(L(NN))]. 2D EXSY cross-peaks were clearly observed between bipy- and acac-hydrogen atoms of the two geometrical isomers of 1-3 as well as between bipy and acac(-) protons of the cis isomer, indicating a dynamic process that corresponds to cis-trans isomerization and a cis-cis racemization. The thermodynamic and kinetic parameters of the equilibrium between these two isomers were calculated for compounds 1 and 2 by using variable temperature (VT) NMR data. Both cis-trans isomerization and cis-cis racemization processes probably proceed with an intramolecular twist mechanism involving a trigonal prismatic transition state. Density functional calculations (DFT) also indicated such a rearrangement mechanism. 相似文献
22.
Tasiopoulos AJ Wernsdorfer W Moulton B Zaworotko MJ Christou G 《Journal of the American Chemical Society》2003,125(50):15274-15275
The compound [CeIVMnIII8O8(O2CMe)12(H2O)4].4H2O (1.4H2O) has been obtained from a template synthesis involving the reaction of the chain polymer {[MnIII(OH)(O2CMe)2] .(MeCO2H).(H2O)}n (3) with Ce(IV). Compound 1 contains a MnIII8 loop inside which is held the Ce(IV) ion by the bridging oxide ions. Magnetization and magnetic susceptibility studies establish that 1 has an S = 16 spin ground state, the largest yet for a Mn cluster, and displays the slow magnetization relaxation and hysteresis behavior of a single-molecule magnet (SMM). It is thus the highest spin Mn SMM discovered to date. 相似文献
23.
Anastasios D. Simalarides 《Periodica Mathematica Hungarica》2000,40(1):71-75
Let be a primitive character mod k, k > 2. In [1], the following elementary estimate
was given, where
by definition. In the present note we sharpen this estimate by a factor 3/4 in the case of an even primitive character , by improving upon the proof given in [1] in a way which does not alter the elementary character of the method. 相似文献
24.
Christos Kokkinos Anastasios Economou Ioannis Raptis Thanasis Speliotis 《Electrochemistry communications》2009,11(2):250-253
This work describes a novel type of antimony electrode for adsorptive stripping voltammetry (AdSV). The electrode was microfabricated by coating a silicon chip with a thin antimony-film by means of sputtering and the active area of the electrode was defined by photolithography. The resulting antimony-film electrodes (SbFEs) were characterized by optical and electrochemical techniques. The sensors were tested for the detection of low concentrations of Ni(II) by AdSV in the presence of dimethylglyoxime. Well-formed stripping peaks and a linear dependence of the stripping peak current on the Ni(II) concentration were observed on the microfabricated SbFEs while comparative measurements attempted with electroplated SbFEs were unsuccessful. Utilizing thin-film technology for the formation of the antimony-film extends the scope of these devices as mercury-free sensors in AdSV. 相似文献
25.
Eleni E. Moushi Theocharis C. Stamatatos Vassilios Nastopoulos George Christou Anastasios J. Tasiopoulos 《Polyhedron》2009,28(9-10):1814-1817
The reaction of [Mn(O2CMe)2] · 4H2O with pdH2 (1,3-propanediol) or mpdH2 (2-methyl-1,3-propanediol) in the presence of NaN3 in MeCN/py (py = pyridine) results in the formation of two new one-dimensional coordination polymers composed of a [MnIII6MnII11(μ4-O)8(μ3-N3)4]25+ octahedral unit. The peripheral ligation is completed by pd2? (or mpd2?), acetate, pyridine and μ-1,3-N3? ligands. The latter bridges each Mn17 unit to its neighboring one, resulting in the formation of the two 1-D coordination polymers. Variable-temperature dc magnetic susceptibility studies indicate the existence of predominantly ferromagnetic interactions and a resulting giant ground state spin within the Mn17 units and intermolecular antiferromagnetic exchange interactions between the neighboring Mn17 units that result in diamagnetic ground spin states for both polymeric compounds. 相似文献
26.
Papatriantafyllopoulou C Stamatatos TC Wernsdorfer W Teat SJ Tasiopoulos AJ Escuer A Perlepes SP 《Inorganic chemistry》2010,49(22):10486-10496
The combined use of the anion of phenyl(2-pyridyl)ketone oxime (ppko(-)) and azides (N(3)(-)) in nickel(II) carboxylate chemistry has afforded two new Ni(II)(5) clusters, [Ni(5)(O(2)CR')(2)(N(3))(4)(ppko)(4)(MeOH)(4)] [R' = H (1), Me (2)]. The structurally unprecedented {Ni(5)(μ-N(3))(2)(μ(3)-N(3))(2)}(6+) cores of the two clusters are almost identical and contain the five Ni(II) atoms in a bowtie topology. Two N(3)(-) ions are end-on doubly bridging and the other two ions end-on triply bridging. The end-on μ(3)-N(3)(-) groups link the central Ni(II) atoms with the two peripheral metal ions on either side of the molecule, while the Ni···Ni bases of the triangles are each bridged by one end-on μ-N(3)(-) group. Variable-temperature, solid-state direct- (dc) and alternating-current (ac) magnetic susceptibility, and magnetization studies at 2.0 K were carried out on both complexes. The data indicate an overall ferromagnetic behavior and an S = 5 ground state for both compounds. The ac susceptibility studies on 1 reveal nonzero, frequency-dependent out-of-phase (χ(M)") signals at temperatures below ~3.5 K; complex 2 reveals no χ(M)" signals. However, single-crystal magnetization versus dc field scans at variable temperatures and variable sweep rates down to 0.04 K on 1 reveal no noticeable hysteresis loops, except very minor ones at 0.04 K assignable to weak intermolecular interactions propagated by nonclassical hydrogen bonds. 相似文献
27.
Malte Brasholz Brian A. Johnson Anastasios Polyzos Simon Saubern John H. Ryan 《Tetrahedron》2010,66(33):6445-1893
A domino cyclization reaction of the bis-unsaturated ketone 3 with hydroxylamine proceeds with good yield and high stereoselectivity, in a flow reactor system. The tricyclic spiropiperidine products 5 and 2 obtained are valuable building blocks for the synthesis of analogues of the histrionicotoxin alkaloids. 相似文献
28.
We consider the problem of characterizing user equilibria and optimal solutions for selfish routing in a given network. We
extend the known models by considering malicious behavior. While selfish users follow a strategy that minimizes their individual
cost, a malicious user will use his flow through the network in an effort to cause the maximum possible damage to the overall cost. We define
a generalized model, present characterizations of flows at equilibrium and prove bounds for the ratio of the social cost of
a flow at equilibrium over the cost when centralized coordination among users is allowed.
An extended abstract of this work appeared in the Proceedings of the 14th Annual International Symposium on Algorithms and
Computation (ISAAC) 2003.
G. Karakostas’ research was supported by an NSERC Discovery research grant and MITACS.
Part of this research was done when Viglas was a postdoctoral fellow at the University of Toronto, Canada. 相似文献
29.
30.
Anastasia N. GeorgopoulouConstantinos G. Efthymiou Constantina PapatriantafyllopoulouVassilis Psycharis Catherine P. RaptopoulouManolis Manos Anastasios J. TasiopoulosAlbert Escuer Spyros P. Perlepes 《Polyhedron》2011,30(18):2978-2986
The synthetic investigation of the NiII/M(NO3)3·6H2O/di-2-pyridyl ketone [(py)2CO] tertiary reaction system in EtOH has yielded triangular Ni2M cationic complexes (M = lanthanide, Y). The reaction between Ln(NO3)3·6H2O, Ni(ClO4)2·6H2O, (py)2CO and base (1:3:3:3) in EtOH under gentle heating gave the isostructural complexes [Ni2Ln{(py)2C(OEt)(O)}3{(py)2C(OH)(O)}(NO3)(H2O)](ClO4)2 (Ln = Gd, 2; Ln = Tb, 3) in high yields. The ligands (py)2C(OEt)(O)− and (py)2C(OH)(O)− are the monoanions of the hemiketal and gem-diol derivatives of (py)2CO, respectively, formed in situ in the presence of the metal ions. The cations of 2 and 3 consist of one 8-coordinate LnIII and two distorted octahedral NiII atoms in an essentially isosceles, triangular arrangement capped by a central μ3-Ο− atom of the unique 3.3011 (Harris notation) (py)2C(OH)(O)− ligand. Each metal-metal edge is bridged by the deprotonated O atom of one 2.2011 (py)2C(OEt)(O)− ligand. The isostructural complexes [Ni2M{(py)2C(OEt)(O)}4(NO3)(H2O)]2[M(NO3)5](ClO4)2 (M = Y, 4 ; M = Tb, 5 ; M = Dy, 6) were prepared by the 1:1 reaction of the mononuclear “metalloligand” [Ni(O2CMe){(py)2CO}{(py)2C(OH)2}](ClO4) (1) and M(NO3)3·6H2O in EtOH under mild heating in moderate to good yields. The structures of the dications of 4-6 are similar to those in 2 and 3, the only difference being the replacement of the unique 3.3011 (py)2C(OH)(O)− ligand of the latter by one 3.3011 (py)2C(OEt)(O)− group in the former. The YIII, TbIII and DyIII atoms in [M(NO3)5]2− are coordinated by five bidentate chelating nitrato groups. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the ligands. Variable temperature, solid-state direct current magnetic susceptibility and magnetization studies were carried out on dried samples of 2-4. The data indicate ferromagnetic Ni?Ni and Ni?Gd exchange interactions, and an ST = 11/2 ground state for 2. Complex 3 is characterized by a high-spin ground state while the ferromagnetic Ni?Ni interaction for 2 is independently supported by the study of 4. No out-of-phase, alternating current susceptibility signals have been detected for 3 that would be indicative of SMM behavior. 相似文献