Search results for "dimer"
showing 10 items of 558 documents
Theoretical studies on the spectroscopy of the 7-azaindole monomer and dimer
2001
The absorption and the emission spectra, both fluorescence and phosphorescence, of the 7-azaindole molecule have been studied by means of the complete active space (CAS) SCF method and multiconfigurational second-order perturbation theory (CASPT2). Excitation energies, oscillator strengths, dipole moments, transition dipole moments, and their directions have been computed and the results compared to those of analogous molecules such as indene, indole, and benzimidazole, to get a homogeneous picture of the photophysics of the systems. The absorption and emission of the 7-azaindole dimer and its related tautomer have also been computed in order to get further insight into the double fluoresce…
Electrochemical reduction properties of A-frame compounds and crystal structure of Pd2(dppm)2(Me)2(Br)+ dimer
2006
Abstract Two series of A-frame complexes, [Pd2(dppm)2(R)2(μ-X)]+ (R = Me and X = Cl, Br, I, H; R = Mes and X = Br, I), were investigated by cyclic voltammetry (CV). The 2-electron reduction potentials for the first series increase from I (−1.10), Br (−1.17), Cl (−1.25) to H (−1.65 V versus SCE, in CHCl3), as well as in the second series; Br (−1.35) and I (−1.38 V versus SCE, in THF). The nature of the LUMO where the electron reduction takes place is qualitatively addressed by DFT on the corresponding model complexes [Pd2(H2PCH2PH2)2(R)2(μ-X)]+. The LUMO and (LUMO + 1) of the halide derivatives exhibit the presence of Pd d x 2 - y 2 atomic orbitals interacting in an anti-bonding fashion with…
Aggregation Behavior of Halogenated Squaraine Dyes in Buffer, Electrolytes, Organized Media, and DNA
2002
Aggregation properties of bis(3,5-dibromo-2,4,6-trihydroxyphenyl)squaraine (1) and bis(3,5-diiodo-2,4,6-trihydroxyphenyl)squaraine (2) have been examined in buffer and in the presence of electrolytes, β-cyclodextrin, micelles and DNA. These dyes were found to form aggregates in buffer and methanol−water solutions that have absorption bands blue-shifted to those of the monomeric forms. The iodo derivative 2 forms aggregates at much lower concentrations (1.7 × 10-6 M) compared to the bromo derivative 1 (2.35 × 10-6 M) in 20% (vol/vol) methanol−buffer solution. Increase in methanol concentration in methanol−water solutions resulted in the disruption of the aggregates. The intermediate dimer in…
Vibrations of weakly coupled nanoparticles
2009
The vibrations of a coupled pair of isotropic silver spheres are investigated and compared with the vibrations of the single isolated spheres. Situations of both strong coupling and also weak coupling are investigated using continuum elasticity and perturbation theory. The numerical calculation of the eigenmodes of such dimers is augmented with a symmetry analysis. This checks the convergence and applicability of the numerical method and shows how the eigenmodes of the dimer are constructed from those of the isolated spheres. The frequencies of the lowest frequency vibrations of such dimers are shown to be very sensitive to the strength of the coupling between the spheres. Some of these mod…
Dynamic Diglyme-Mediated Self-Assembly of Gold Nanoclusters
2015
We report the assembly of gold nanoclusters by the nonthiolate ligand diglyme into discrete and dynamic assemblies. To understand this surprising phenomenon, the assembly of Au20(SC2H4Ph)15-diglyme into Au20(SC2H4Ph)15-diglyme-Au20(SC2H4Ph)15 is explored in detail. The assembly is examined by high-angle annular dark field scanning transmission electron microscopy, size exclusion chromatography, mass spectrometry, IR spectroscopy, and calorimetry. We establish a dissociation constant for dimer to monomer conversion of 20.4 μM. Theoretical models validated by transient absorption spectroscopy predict a low-spin monomer and a high-spin dimer, with assembly enabled through weak diglyme oxygen-g…
Anisotropic exchange coupling in the Keggin derivative K8[Co2(D2O)(W11O39)] · n D2O
1998
Abstract 20 g of the fully deuterated title compound have been prepared in polycrystalline form and investigated by inelastic neutron scattering using both thermal and cold neutrons. Magnetic dimer excitations were observed and the energy-splitting pattern resulting from the exchange coupling within the Co 2+ dimer was determined. The coupling is highly anisotropic with the parameter values J =−2.24 meV and η =0.33 based on the effective coupling Hamiltonian H =−2J[S 1z S 2z +η(S 1x S 2x +S 1y S 2y )] . The anisotropy results mainly from the single-ion anisotropy of the Co 2+ ion in the distorted octahedral coordination.
First donor stabilized-phosphenium copper(I) complexes
2012
Abstract The preliminary studies of coordination properties of one donor stabilized-phosphenium adduct have been explored in copper chemistry. The preparation as well as the characterization of first examples of donor stabilized-phosphenium copper(I) complexes is reported in the paper. Thus, the direct addition of CuBr.SMe2 to an equivalent amount of cationic P‐ligands (L1+ or L2+)(PF6), with and , following by a crystallization in acetonitrile/Et2O led to first copper complexes [(L1,2+)CuBr2−] 1 and 3 and [(L1,2+)Cu+(NCMe)3+](PF6−)2 2 and 4 in a 1:1 ratio. However, when DMF/Et2O mixture was used as crystallization solvent, a stable bromo-bridged copper(I) dimer 5 [(L2+)CuBr(DMF)]2 was obta…
Reactions of pyridine-2-carbaldimines with chloro-bridged palladium(II) and platinum(II) 2-methylallyl dimers. Solution behaviour of the cationic com…
1987
Abstract The reactions of pyridine-2-carbaldimines, py-2- CHNR (R = C6H4OMe-p, Me), with allylic dimers [MCl(n3-2-MeC3H4)]2 give rise to stoichiometry, concentration, solvent and temperature dependent equilibria, in which the cationic complexes [M(n3- 2-MeC3H4)(py-2-CHNR)]+ and the anion [MCl2(n3- 2-MeC3H4)]- or Cl- are involved. In general, the ligand/dimer reaction (1/1 molar ratio) yields the ionic products [M(n3-2-MeC3H4)(py-2-CHNR)]- [MCl2(n3-2-MeC3H4)], which can be isolated as solids, whereas the same reaction in a 1/0.5 molar ratio yields the species [M(n3-2-MeC3H4 )(py-2-CH NR)] Cl, which can be studied only in solution, but are easily converted into [M(n3-2-MeC3H4)(py-2-CH NR…
Crystal structure, magnetic and spectroscopic properties of copper(II) formato dimethylformamide: a new tetracarboxylato-bridged copper(II) dimer
2002
Abstract The crystal and molecular structure of a new tetracarboxylato copper(II) dimer [bis(dimethylformamide)tetrakis(μ-formato)dicopper(II)], has been determined by X-ray diffraction methods. The crystal structure consists of a centrosymmetric dimer [Cu2(HCOO)4(dmf)2], where four bidentate formato anions form syn–syn bridges between the metal ions which are in a 4+1 environment. Magnetic susceptibility data show that the copper ions are strongly antiferromagnetically coupled with J=−470 cm−1. The EPR spectrum shows a characteristic pattern of a triplet state with a D zero field splitting value of 0.27 cm−1.
Versatile redox reactivity of triaryl-meso-substituted Ni(ii) porphyrin
2014
The electrochemical oxidation of nickel(II) 5,15-p-ditolyl-10-phenylporphyrin (1-Ni) leads to the formation of different coupling products, with the distribution depending on the nature of the solvent (CH2Cl2–CH3CN, CH2Cl2, DMF), the cell configuration (2 or 3 compartments) and the number of electrons abstracted. In a two compartment configuration (anode and cathode in the same compartment) in a CH2Cl2–CH3CN mixture, nickel(II) 5-chloro-10,20-p-ditolyl-15-phenylporphyrin (1-Ni-Cl) was isolated in good yield and its mechanism of formation is proposed. Switching to the three compartment configuration, the meso-β/meso-β doubly fused dimer (3-Ni) is detected as the major product whereas in pure…