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11.
Madeleine Gasperin 《Journal of solid state chemistry》1985,60(3):316-319
β-Na2UO4 single crystals were synthesized from a melt with U, Nb, and Na ions. They are orthorhombic Fmmm with a = 5.802(2), B = 5.969(2), and c = 11.699(3) Å, and Z = 4. The structure was refined to R = 0.075 and Rw = 0.096 for 603 independent reflexions with I ≥ 3σ(I). The study shows that Na and O atoms are delocalized and that the structure results from the juxtaposition of four P21/b domains. 相似文献
12.
The condensation of ethyl trifluoroacetoacetate with various heterocyclic amines yielded 2-(trifluoromethyl)phenanthrolin-4-ones. The structures of these compounds were established from a study of their infrared and ultraviolet spectra. Substituted phenanthrolines were prepared by nucleophilic attack on a chlorophenanthroline. The oxidation of 5-methoxy-2-trifluoromethyl-1,10-phenanthroline yielded an o-quinone which was treated with typical quinone reagents. A molecular orbital calculation was carried out in an attempt to explain the ease of reduction of the 1,10-phenanthroline system and the colors of the reduced compounds. 相似文献
13.
Madeleine Gasperin 《Journal of solid state chemistry》1984,53(1):144-147
TiNb2O7 is monoclinic with a = 20.351(3), b = 3.801(2), c = 11.882(2) Å, β = 120.19°, Z = 6. The structure, determined by Wadsley in 1961 from visual estimation of intensities, has been refined to R = 0.065 for 915 reflexions with I ≥ 3σI. This study shows that Ti and Nb are not randomly distributed: like several niobo or tantalotitanates with edge-sharing octahedra, this one shows preferential occupation of one type of site by the titanium atoms. 相似文献
14.
Luigi R. Nassimbeni Sevi Papanicolaou Madeleine H. Moore 《Journal of inclusion phenomena and macrocyclic chemistry》1986,4(1):31-42
The structures of Ni(NCS)2(4-PhPy)4·4DMSO and Ni(NCS)2(3-MePy)4·CHCl3 have been elucidated. Movement of guest molecules through channels in the host structure was simulated by potential energy calculations. Ni(NCS)2(3,5-diMePy)4 does not form inclusion compounds. An intra-molecular potential energy study shows that theortho-hydrogens on the 3,5-dimethylpyridine ligands control the conformation of the molecule. The same result is obtained with the 4-methylpyridine ligand, which suggests that the extent of rotation of substituted pyridines about the Ni–N bounds is not a factor governing clathrate formation.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82030 (43 pages). 相似文献
15.
Gaunt AJ May I Helliwell M Richardson S 《Journal of the American Chemical Society》2002,124(45):13350-13351
The reaction between PW9O349- and NpO2+ has yielded the first structurally characterized neptunyl(V) polyoxometalate complex, [Na2(NpO2)2(A-PW9O34)2]14-. This complex is isostructural with the uranyl(VI) analogue, and there is also spectroscopic evidence for its existence in solution. The complex is readily extracted into toluene, and this may have significance in the sequestering and/or separation of the neptunyl ion in terms of nuclear waste management. 相似文献
16.
Bhatt AI May I Volkovich VA Collison D Helliwell M Polovov IB Lewin RG 《Inorganic chemistry》2005,44(14):4934-4940
The reduction of selected lanthanide cations to the zerovalent state in the room-temperature ionic liquid [Me3N(n)Bu][TFSI] is reported (where TFSI = bistriflimide, [N(SO2CF3)2]-). The lanthanide cations were introduced to the melt as the TFSI hydrate complexes [Ln(TFSI)3(H2O)3] (where Ln = La(III), Sm(III) or Eu(III)). The lanthanum compound [La(TFSI)3(H2O)3] has been crystallographically characterized, revealing the first structurally characterized f-element TFSI complex. The lanthanide in all three complexes was shown to be reducible to the metallic state in [Me3N(n)Bu][TFSI]. For both the Eu and Sm complexes, reduction to the metallic state was achieved via divalent species, and there was an additional observation of the electrodeposition of Eu metal. 相似文献
17.
Mireia Segado Centellas Madeleine Piot Raphaël Salles Anna Proust Ludovic Tortech Dalil Brouri Sbastien Hupin Benjamin Abcassis David Landy Carles Bo Guillaume Izzet 《Chemical science》2020,11(40):11072
The formation of hierarchical nanostructures using preformed dumbbell-like species made of covalent organic–inorganic polyoxometalate (POM)-based hybrids is herein described. In this system, the presence of charged subunits (POM, metal linkers, and counter ions) in the complex molecular architecture can drive their aggregation, which results from a competition between the solvation energy of the discrete species and intermolecular electrostatic interactions. We show that the nature of the POM and the charge of the metal linker are key parameters for the hierarchical nanoorganization. The experimental findings were corroborated with a computational investigation combining DFT and molecular dynamics simulation methods, which outlines the importance of solvation of the counter ion and POM/counter ion association in the aggregation process. The dumbbell-like species can also form gels, in the presence of a poorer solvent, displaying similar nanoorganization of the aggregates. We show that starting from the designed molecular building units whose internal charges can be controlled by redox trigger we can achieve their implementation into soft nanostructured materials through the control of their supramolecular organization.The formation of hierarchical nanostructures using supramolecular dumbbell-like species made of organic–inorganic polyoxometalate-based hybrids is investigated by combination of SAXS and computational methods. 相似文献
18.
Jiang J Sarsfield MJ Renshaw JC Livens FR Collison D Charnock JM Helliwell M Eccles H 《Inorganic chemistry》2002,41(10):2799-2806
Eight uranyl compounds containing the dicarboxylate ligands iminodiacetate (IDA) or oxydiacetate (ODA) have been characterized in the solid state. The published polymeric structures for [UO(2)(C(4)H(6)NO(4))(2)] and [UO(2)(C(4)H(4)O(5))](n) have been confirmed, while Ba[UO(2)(C(4)H(5)NO(4))(2)] x 3H(2)O, [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)][UO(2)(C(4)H(4)O(5))(2)] [orthorhombic space group Pnma, a = 10.996(5) A, b = 21.42(1) A, c = 8.700(3) A, Z = 4], and [C(2)H(5)NH(2)(CH(2))(2)NH(2)C(2)H(5)][UO(2)(C(4)H(4)O(5))(2)] [monoclinic space group P2(1)/n, a = 6.857(3) A, b = 9.209(5) A, c = 16.410(7) A, beta = 91.69(3), Z = 2] contain monomeric anions. The distance from the uranium atom to the central heteroatom (O or N) in the ligand varies. Crystallographic study shows that U-heteroatom (O/N) distances fall into two groups, one 2.6-2.7 A in length and one 3.1-3.2 A, the latter implying no bonding interaction. By contrast, EXAFS analysis of bulk samples suggests that either a long U-heteroatom (O/N) distance (2.9 A) or a range of distances may be present. Three possible structural types, two symmetric and one asymmetric, are identified on the basis of these results and on solid-state (13)C NMR spectroscopy. The two ligands in the complex can be 1,4,7-tridentate, giving five-membered rings, or 1,7-bidentate, to form an eight-membered ring. (C(4)H(12)N(2))[(UO(2))(2)(C(4)H(5)NO(4))(2)(OH)(2)] x 8H(2)O [monoclinic space group P2(1)/a, a = 7.955(9) A, b = 24.050(8) A, c = 8.223(6) A, beta = 112.24(6), Z = 2], (C(2)H(10)N(2))[(UO(2))(2)(C(4)H(5)NO(4))(2)(OH)(2)] x 4H(2)O, and (C(6)H(13)N(4))(2)[(UO(2))(2)(C(4)H(4)O(5))(2)(OH)(2)] x 2H(2)O [monoclinic space group C2/m, a = 19.024(9) A, b = 7.462(4) A, c = 2.467(6) A, beta = 107.75(4), Z = 4] have a dimeric structure with two capping tridentate ligands and two mu(2)-hydroxo bridges, giving edge-sharing pentagonal bipyramids. 相似文献
19.
Cammidge AN Nekelson F Helliwell M Heeney MJ Cook MJ 《Journal of the American Chemical Society》2005,127(47):16382-16383
A mixed condensation of a substituted and unsubstituted silicon phthalocyanine monomer, in which the former serves as a "cap" to a growing oligomeric chain, provides unprecedented access to a mixed dimer, trimers, and a tetramer. An important element of product control can be achieved by changing the ratio of the precursor monomers. 相似文献
20.
Allen CM Langlois R Sharman WM La Madeleine C Van Lier JE 《Photochemistry and photobiology》2002,76(2):208-216
Photodynamic therapy (PDT) is a promising treatment modality that has recently been accepted in clinics as a curative or palliative therapy for cancer and other nonmalignant conditions. Phthalocyanines (Pc) are attractive photosensitizers for PDT because of their enhanced photophysical and photochemical properties. The overall charge and solubility of Pc play a major role in their potential usefulness for PDT. A series of amphiphilic derivatives of tetrasulfonated aluminum Pc (AlPcS4) was prepared by substituting one of the four sulfonate groups with aliphatic side chains of 4, 8, 12 and 16 carbon atoms. The photodynamic properties of the derivatives were compared with those of AlPcS4 and the adjacent disulfonated aluminum Pc. Parameters studied included reversed-phase high-performance liquid chromatography (HPLC) retention times, capacity to generate singlet oxygen (1O2), in vitro cell uptake and phototoxicity, as well as PDT response of transplantable EMT-6 tumors in mice. The monomerized AlPcS4 derivatives showed similar or higher capacities to generate 1O2 as compared with the parent AlPcS4 as measured from relative L-tryptophan photooxidation yields. A549 cell uptake of the AlPcS4 derivatives decreased in the following order: AlPcS4(C16) > AlPcS4(C12) > AlPcS4(C8) > AlPcS4(C4). Human low-density lipoprotein at high concentrations (40 micrograms/mL) completely prevented uptake, whereas at 4 micrograms/mL uptake was decreased for the more lipophilic compounds and yet remained unaffected for the more hydrophilic dyes. Using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, A549 cell survival was assessed; it showed that photocytotoxic activity varied directly with the HPLC retention times, i.e. more hydrophilic compounds were less phototoxic. As 1O2 yields were similar for the four substituted AlPcS4 derivatives, it was postulated that the increased cytotoxic activity was caused by enhanced subcellular localization as a result of the long aliphatic side chains. These amphiphilic compounds proved to be photodynamically potent against the EMT-6 mouse mammary tumor model implanted in Balb/c mice. At dye doses of 0.2 mumol/kg and a fluence of 400 J/cm2 complete tumor regression was observed with no morbidity. The substitution of AlPcS4 with long aliphatic chains on the macrocycle greatly enhances its photodynamic efficacy both in vitro and in vivo. 相似文献