Photophysics of monodisperse platinum-acetylide oligomers: delocalization in the singlet and triplet excited states

A series of monodisperse Pt-acetylide polymers that contain the [-CC-(p-C6H4)-CC-(t-Pt(PBu3)2)-]n repeat unit has been prepared for n = 1, 2, 3, 4, 5, and 7. The photophysical properties of the series provide information concerning the relationship between the oligomer length and delocalization in the singlet and triplet excited states of the pi-conjugated electron system. The results imply that the singlet excited state is delocalized over approximately 6 repeat units; however, the triplet state is considerably more localized. The triplet energy is almost invariant with oligomer length, but the phosphorescence spectra and triplet nonradiative decay rates indicate that the electron-vibrational coupling in the triplet state decreases with increasing oligomer length.     

Radiolysis of Aqueous Solutions of Benzoate Ion: A Radiation Chemistry Experiment for Undergraduates

This investigation describes the chemical effects of ionizing radiation on dilute aqueous solutions of benzoate ion. We have composed an experimental procedure that allows undergraduate chemistry students to identify and to quantitatively determine the amount of the products that are produced. The student investigators determine the absorbed dose that a sample receives when exposed to a ⁶⁰Co source, irradiate dilute aqueous solutions of benzoate ion, and analyze the resulting mixture of hydroxybenzoate ions using high-performance liquid chromatography. The radiolysis of dilute solutions of benzoate ion results in the formation of a mixture of ortho-, meta-, and para-hydroxybenzoate ions that are readily separated on a C₁₈ -Bondapak column. By the use of appropriate calibration curves, the yield (G values) of each of the isomers may be determined and compared.This paper was presented at the 15th Biennial Conference on Chemical Education, Waterloo, Ontario, Canada, August 1998 by N. Zevos and at the 26th Northeast Regional Meeting of the American Chemical Society by Evon Powell.     

The crystal structure of 3-R Nb1.06S2

The X-ray single crystal structure of 3-R Nb_1.06S₂ has been determined. The material crystallizes in the space group R_3m with a = 3.3285(4) and c = 17.910(4) Å when indexed on a hexagonal lattice. The structure was refined by full matrix least squares procedures to a final residual of R = 0.026 based on 79 observed (I > 3σ_I) reflections. The sulfurs form closest-packed layers with the majority of the metal in sheets of trigonal prismatic sites. A small portion of niobium was found to occupy octahedral sites, between the van der Waals gaps of the sulfur lattice. Niobium in the van der Waals region is trigonally distorted from octahedral symmetry, with niobium-sulfur distances of 2.234(8) and 2.577(11) Å, because of repulsion from niobium in adjacent trigonal prismatic layers.     

Energy transfer in rare earth-doped CaWO4 after red edge excitation

Host sensitized energy transfer in CaWO₄ doped with Eu³⁺ and Sm³⁺ is investigated using pulsed laser time-resolved spectroscopy techniques. The excitation is into the long wavelength tail of the absorption edge and the results indicate that this selectively excites tungstate ions which are located next to activator impurity ions. The subsequent energy transfer is found to be consistent with a single step, nearest neighbor process. Both electric dipole-dipole and exchange interactions can predict strong enough transfer to account for the observed rates. These results are compared to those obtained previously for broad band excitation into the highest energy absorption bands of CaWO₄ crystals.     

The dynamic stereochemistry of the allylic ligand in a μ-allylic complex of platinum(II)

¹H NMR studies of an equilibrium mixture of 1,1,1,5,5,5-hexafluoropentane-2,4-dionato-π-allylplatinum(II) [IA] and bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)bis(μ-allyl)diplatinum(II) [IB] show that the μ-allylic ligands of (IB) exhibit temperature dependent tautomeric behaviour, giving rise to a site-exchange between protons on these ligands.