showing 3 related works from this author
Helicate Extension as a Route to Molecular Wires
2008
We describe the preparation of a helicate containing four closely spaced, linearly arrayed copper(I) ions. This product may be prepared either directly by mixing copper(I) with a set of precursor amine and aldehyde subcomponents, or indirectly through the dimerization of a dicopper(I) helicate upon addition of 1,2-phenylenediamine. A notable feature of this helicate is that its length is not limited by the lengths of its precursor subcomponents: each of the two ligands wrapped around the four copper(I) centers contains one diamine, two dialdehyde, and two monoamine residues. This work thus paves the way for the preparation of longer oligo- and polymeric structures. DFT calculations and elec…
The electronic spectra of 2-(2′-hydroxybenzoyl)pyrrole and 2-(2′-methoxybenzoyl)pyrrole: a theoretical study
2005
The gas-phase electronic spectra of 2-(2 0 -hydroxybenzoyl)pyrrole and 2-(2 0 -methoxybenzoyl)pyrrole have been determined using multiconfigurational perturbation theory (CASPT2). Solvatochromic spectral shifts for these molecules have been measured in cyclohexane and methanol and the electrostatic components of these shifts have been estimated using the vertical electrostatic model (VEM 4.2) developed for the configuration interaction with single excitations model implemented with the intermediate neglect of differential overlap Hamiltonian (CIS/INDO/ S2). Comparison between theory and experiment and an interpretation of the main spectral differences between the two substituted pyrroles an…
Theoretical characterization of end-on and side-on peroxide coordination in ligated Cu2O2 models.
2006
The relative energetics of mu-eta1:eta1 (trans end-on) and mu-eta2:eta2 (side-on) peroxo isomers of Cu2O2 fragments supported by 0, 2, 4, and 6 ammonia ligands have been computed with various density functional, coupled-cluster, and multiconfigurational protocols. There is substantial disagreement between the different levels for most cases, although completely renormalized coupled-cluster methods appear to offer the most reliable predictions. The significant biradical character of the end-on peroxo isomer proves problematic for the density functionals, while the demands on active space size and the need to account for interactions between different states in second-order perturbation theor…