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91.
Floquet S Ouali N Bocquet B Bernardinelli G Imbert D Bünzli JC Hopfgartner G Piguet C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(8):1860-1875
The segmental tris-tridentate ligand L7 reacts with stoichiometric quantities of Ln(III) (Ln=La-Lu) in acetonitrile to give the complexes [Ln(2)(L7)(3)](6+) and [Ln(3)(L7)(3)](9+). Formation constants point to negligible size-discriminating effects along the lanthanide series, but Scatchard plots suggest that the self-assembly of the trimetallic triple-stranded helicates [Ln(3)(L7)(3)](9+) is driven to completion by positive cooperativity, despite strong intermetallic electrostatic repulsions. Crystallization provides quantitatively [Ln(3)(L7)(3)](CF(3)SO(3))(9) (Ln=La, Eu, Gd, Tb, Lu) and the X-ray crystal structure of [Eu(3)(L7)(3)](CF(3)SO(3))(9).(CH(3)CN)(9).(H(2)O)(2) (Eu(3)C(216)H(226)N(48)O(35)F(27)S(9), triclinic, P1, Z=2) shows the three ligand strands wrapped around a pseudo-threefold axis defined by the three metal ions rigidly held at about 9 A. Each metal ion is coordinated by nine donor atoms in a pseudo-trigonal prismatic arrangement, but the existence of terminal carboxamide units in the ligand strands differentiates the electronic properties of the terminal and the central metallic sites. Photophysical data confirm that the three coordination sites possess comparable pseudo-trigonal symmetries in the solid state and in solution. High-resolution luminescence analyses evidence a low-lying LMCT state affecting the central EuN(9) site, so that multi-metal-centered luminescence is essentially dominated by the emission from the two terminal EuN(6)O(3) sites in [Eu(3)(L7)(3)](9+). New multicenter equations have been developed for investigating the solution structure of [Ln(3)(L7)(3)](9+) by paramagnetic NMR spectroscopy and linear correlations for Ln=Ce-Tb imply isostructurality for these larger lanthanides. NMR spectra point to the triple helical structure being maintained in solution, but an inversion of the magnitude of the second-rank crystal-field parameters, obtained by LIS analysis, for the LnN(6)O(3) and LnN(9) sites with respect to the parameters extracted for Eu(III) from luminescence data, suggests that the geometry of the central LnN(9) site is somewhat relaxed in solution. 相似文献
92.
Suárez S Mamula O Imbert D Piguet C Bünzli JC 《Chemical communications (Cambridge, England)》2003,(11):1226-1227
Complexes between lanthanide nitrates and a pro-mesogenic 18-membered diaza-substituted coronand are luminescent both as powders and liquid crystals (between 87 and 195 degrees C), and the phase transitions are detected by monitoring luminescence intensity and lifetime. 相似文献
93.
94.
Henry-dit-Quesnel A Toupet L Pommelet JC Lequeux T 《Organic & biomolecular chemistry》2003,1(14):2486-2491
The synthesis of difluoromethylphosphonates is becoming difficult due to environmental protective laws restricting the use of HCFCs and CFCs as starting chemicals. To circumvent this limitation, we report the preparation of a thioether as a new source of the lithiodifluoromethylphosphonate. This methodology avoiding the use of HCFCs involves a selective fluorination of sulfide followed by a thiaphilic addition of an organometallic reagent, which offers an alternative route to obtain phosphonodifluoromethyl carbanion. A contrasted reactivity, due to a medium effect, was also noted which allows addition of a wide range of electrophiles including nitroalkenes and DMF to thioethers. 相似文献
95.
Petoud S Cohen SM Bünzli JC Raymond KN 《Journal of the American Chemical Society》2003,125(44):13324-13325
Efficient lanthanide (Ln) luminescent probes require good ligand-to-metal energy transfer and high aqueous stability. A family of ligands based on 2-hydroxyisophthalamide chelating units is reported. These form highly stable, eight-coordinate Ln complexes. Several of these (Ln = Sm, Eu, Tb, Dy) emit in the visible region with good ligand-to-lanthanide energy transfer. The absolute quantum yields of the two Tb complexes studies (Phi = 0.59, 0.61) and high absorbance make these the brightest luminescent probes for time-resolved detection; the emission spectrum of one complex can be seen down to 10-15 M. The low overlap of the four different Ln complexes enables their simultaneous detection and discrimination. 相似文献
96.
Christopher W. Doble Jean-Paul Doignon Jean-Claude Falmagne Peter C. Fishburn 《Order》2001,18(4):295-311
One of the standard axioms for semiorders states that no three-point chain is incomparable to a fourth point. We refer to asymmetric relations satisfying this axiom as almost connected orders or ac-orders. It turns out that any relation lying between two weak orders, one of which covers the other for inclusion, is an ac-order (albeit of a special kind). Every ac-order is bracketed in a natural way by two weak orders, one the maximum in the set of weak orders included in the ac-order, and the other minimal, but not necessarily the minimum, in the set of weak orders that include the ac-order. The family of ac-orders on a finite set with at least five elements is not well graded (in the sense of Doignon and Falmagne, 1997). However, such a family is both upgradable and downgradable, as every nonempty ac-order contains a pair whose deletion defines an ac-order on the same set, and for every ac-order which is not a chain, there is a pair whose addition gives an ac-order. 相似文献
97.
The electroreduction of a mixture of SO2 and CF3Br in DMF, in an undivided cell with a soluble anode (Mg or Zn) lead to salt of trifluoromethane sulfinic acid in high yield. 相似文献
98.
Nucleophilic para-fluorination of substituted anilines to afford 4-fluorocyclohexadieneimine derivatives is achieved in the presence of hypervalent iodine and pyridinium polyhydrogen fluoride. 相似文献
99.
Jean-Claude Tabet Chantal Prevost Anne Bouillot Josette Bastard Due Do Khae Manh Yves Tondeur 《Helvetica chimica acta》1986,69(4):806-815
A stereospecific and regioselective SN2 mechanism (Walden inversion) is observed during studies involving modified terpenoid epimeric diols in a high-pressure ion source using ammonia as a reagent gas. 相似文献
100.
This article covers 50 years of coordination chemistry of transition metal complexes and metal-sulfur aggregates involving thiolate-incorporating ligands by reviewing selected examples. The studies in the coordination chemistry of sulfur-rich ligands have been undoubtedly triggered and fed by the concomitant development of bioinorganic chemistry, particularly of iron-sulfur enzymes. The review is broken down in five sections, which examine complexes of increasing nuclearity, including binuclear complexes based on compartmental macrocyclic ligands. We show also how ligand engineering has allowed the researchers in the field to control the nuclearity of the complexes, which was a particularly difficult task for sulfur-based ligands, as thiolates show a strong tendency to coordinate to more than one metal cation at once. 相似文献