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Counterion influence on the N–I–N halogen bond
2015
A detailed investigation of the influence of counterions on the [N–I–N]+ halogen bond in solution, in the solid state and in silico is presented. Translational diffusion coefficients indicate close attachment of counterions to the cationic, three-center halogen bond in dichloromethane solution. Isotopic perturbation of equilibrium NMR studies performed on isotopologue mixtures of regioselectively deuterated and nondeuterated analogues of the model system showed that the counterion is incapable of altering the symmetry of the [N–I–N]+ halogen bond. This symmetry remains even in the presence of an unfavorable geometric restraint. A high preference for the symmetric geometry was found also in …
Syntheses, structures and magnetic properties of cyano-bridged one-dimensional Ln3+–Fe3+ (Ln = La, Dy, Ho and Yb) coordination polymers
2019
Four new heterometallic one-dimensional coordination polymers with formulae trans-[La(o-phen)3(H2O)(μ-CN)2Fe(CN)4]·7H2O (1) and trans-[Ln(H2O)2(phen)2(μ-CN)2Fe(CN)4]·nH2O [Ln/n = Dy/8 (2), Ho/7 (3) and Yb/7 (4), (o-phen = 1,10-phenanthroline)] have been synthesized by reacting Ln(NO3)3·xH2O with K3[Fe(CN)6] and 1,10-phenanthroline. The structures of 1–4 have been established by single crystal X-ray diffraction. Polymer 1 presents a chain structure with three o-phen ligands coordinated to La3+ and [Fe(CN)6]3− complexes connecting them through two trans CN− ligands to form a linear chain. Compounds 2–4 are solvates and contain Ln3+ ions coordinated to two o-phen ligands and also bridged by [F…
Synthesis, characterization and thermal properties of small R2R′2N+X−-type quaternary ammonium halides
2005
Twenty-one R {sub 2} R {sup '} {sub 2}N{sup +} X {sup -} -type (R=methyl or ethyl, R {sup '}=alkyl, X=Br or I) quaternary ammonium (QA) halides have been prepared by using a novel one-pot synthetic route in which a formamide (dimethyl-, diethylformamide, etc.) is treated with alkyl halide in the presence of sodium or potassium carbonate. The formation of QA halides was verified with {sup 1}H-NMR, {sup 13}C-NMR, MS and elemental analysis. The crystal structures of four QA halides (two bromide and two iodide) were determined using X-ray single crystal diffraction, and the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bu…
An Unusual Geometry of Five-Coordinate Copper(II): The Structure of Cu(terpy)I2 and Spectroscopic Investigations of Complexes Cu(terpy)X2 (X: I, NCS)
1991
The structure of the compound Cu(terpy)I2 (terpy 2,2′: 6′, 2″ terpyridine) was determined at room temperature. It is monoclinic, space group I2/c with a = 13.689(3), b = 9.510(2), c = 11.605(3) Å, β = 97.59(4)° and Ζ = 4. The copper(II) ions are five-coordinated by the three nitrogen atoms from the terpy ligand and the two iodine atoms. The CuN3I2 polyhedron exhibits the same unusual “reverse” geometry as is observed for Cu(terpy)(NCS)2. Single crystal EPR measurements of the iodide and the isothio-cyanate complexes confirmed the structural results, excluding the possibility of a dynamically averaged geometry.
A series of lanthanide(iii) metal-organic frameworks derived from a pyridyl-dicarboxylate ligand: single-molecule magnet behaviour and luminescence p…
2020
The reactions of LnIII ions with a versatile pyridyl-decorated dicarboxylic acid ligand lead to the formation of a series of novel three-dimensional (3D) Ln-MOFs, [Ln3(pta)4(Hpta)(H2O)]·xH2O (Ln = Dy (1), Eu (2), Gd (3), Tb (4), H2pta = 2-(4-pyridyl)-terephthalic acid, x = 6 for 1, 2.5 for 2, 1.5 for 3 and 2 for 4). The Ln3+ ions act as nine-coordinated muffin spheres, linking to each other to generate trinuclear {Ln3(OOC)6N2} SBUs, which are further extended to be interesting 3D topological architectures. To the best of our knowledge, the Dy-MOF exhibits zero-field single-molecule magnet (SMM) behaviour with the largest effective energy barrier among the previously reported 3D MOF-based Dy…
A Co-monosubstituted Keggin polyoxometalate with an antenna ligand and three cobalt(II) chains as counterion
2009
Abstract A Co-monosubstituted Keggin polyoxometalate with an antenna ligand linked to the Co(II) center with a Co(II)-containing cation has been prepared. The title compound, formulated as {Co(H 2 O) 4 (4,4′-bpy)} 2 (4,4′-Hbpy) 2 [SiW 11 Co(4,4′-bpy)O 39 ] · 5H 2 O ( 1 ) (4,4′-bpy = 4,4′-bipyridine), was synthesized and characterized by elemental analysis, IR spectra, TG analysis, X-ray single crystal structure analysis and magnetic measurements. As far as we know, the title compound represents the first Co(II) substituted Keggin polyoxometalate with an antenna ligand structurally and magnetically characterized.
Effect of phosphatydylcholine on spectral properties and photostability of 3,3′-diethyloxadicarbocyanine iodide (DODCI) — a potent anti-tumor photose…
1998
Abstract The potential anti-tumor photosensitizer 3,3′-diethyloxadicarbocyanine iodide (DODCI) has been immobilized in dimyristoyl phosphatidylcholine (DMPC) vesicles. Binding of the dicarbocyanine to the lipid vesicles induces several changes in the electronic absorption, emission and excitation spectra of the dye. The monomeric dye molecules exist in at least two forms when immobilized in the DMPC liposomes and the non-luminescing H-aggregates of the dye show efficient excitation energy transfer to the DODCI monomers. Entrapment of the dye in the liposomes generally decreases the photostability of DODCI. While emission from singlet oxygen (1O2) has not been recorded, indirect results sugg…
Chapter 2 Single molecule spectroscopy of multichromophoric dendrimers at room and liquid helium temperatures
2004
Publisher Summary This chapter discusses the single molecule spectroscopy of multichromophoric dendrimers at room and liquid helium temperatures. Single molecule spectroscopy has become an important tool for the optical study of the electronic interactions of proximate chromophores as the electronic interactions can be studied without averaging over the properties of an intrinsically heterogeneous ensemble. Single perylenemonoimide (PMI) chromophores are selectively addressed in the frequency domain within spatially isolated multichromophoric dendrimers, which are dispersed in a polymer film. Although the chromophores are interacting, they still can be addressed separately. This feature in …
A new oleanane glycoside from the roots ofAstragalus caprinus
2006
A novel oleanane-type triterpene saponin (1) together with two known molecules, soyasapogenol B and astragaloside VIII were isolated from the roots of Astragalus caprinus. Their structural elucidation was performed mainly by 2D NMR techniques (COSY, TOCSY, NOESY, HSQC, HMBC) and mass spectrometry. Compound 1 was determined as 3-O-[alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucuronopyranosyl]-22-O-beta-D-apiofuranosyl-soyasapogenol B.
Positron Annihilation in Alkali Halides at Low Temperatures
1986
We report on low-temperature positron studies for pure, single crystals of the alkali halides KCl, NaCl and NaF. Strong temperature dependences are observed in the lifetime and angular correlation measurements in the temperature range 10–300 K. Delocalized para-positronium is observed at low temperatures in the three crystals. The broadening, with rising temperature, of the narrow peak in the angular correlation curve can be accounted for by the self-trapping model of positronium. The results are discussed in the light of this model, in terms of positronium localization at imperfections and in terms of positron interactions with imperfections created in the spur of the positron. The increas…