A magnetostructural correlation (conformational electron spin exchange modulation) within an isostructural series of biradical complexes is presented. X-ray crystal structures, variable-temperature electron paramagnetic resonance spectroscopy, zero-field splitting parameters, and variable-temperature magnetic susceptibility measurements were used to evaluate molecular conformation and electron spin exchange coupling in this series of molecules. Our combined results indicate that the ferromagnetic portion of the exchange couplings occurs via the cross-conjugated pi-systems, while the antiferromagnetic portion occurs through space and is equivalent to incipient bond formation. Thus, molecular conformation controls the relative amounts of ferro- and antiferromagnetic contributions to exchange coupling. In fact, the exchange parameter correlates with average semiquinone ring torsion angles via a Karplus-Conroy-type relation. Because of the natural connection between electron spin exchange coupling and electronic coupling related to electron transfer, we also correlate the exchange parameters in the biradical complexes to mixed valency in the corresponding quinone-semiquinone radical anions. Our results suggest that delocalization in the cross-conjugated, mixed-valent radical anions is proportional to the ferromagnetic contribution to the exchange coupling in the biradical oxidation states.

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Red deer Cervus elaphus of the endangered populations from Sardinia and Mesola Wood, northern Italy, were analysed for genetic variation at 531 bp of the mitochondrial control region and 12 polymorphic nuclear microsatellite loci. A phylogenetic analysis was conducted including additional data from the literature to gain insight into the phylogeographical origin of the Sardinian subspecies C. e. corsicanus . Microsatellite variation was low in both populations but Sardinia showed comparatively high variability at the control region. Management recommendations are discussed. In particular, the Mesola red deer, the only remaining indigenous Italian population, ought to be managed to increase the effective population size and should be subdivided into two or more populations. As to the phylogeography of the Sardinian population, microsatellite data favoured mainland Italy as the place of origin in that Sardinia and Mesola showed the smallest distance values and were paired together in trees with high bootstrap support. However, the mitochondrial data only partially confirmed this conclusion but showed great similarity between Sardinian and Spanish red deer. Possible explanations for this discrepancy and general limits of mitochondrial sequences in resolving demographic and biogeographical processes of the recent past are discussed.

The molecular structures and magnetic properties of six dinitroxide biradicals are described. Five of the dinitroxides are trimethylenemethane-type (TMM-type) biradicals; that is, the intramolecular exchange parameter, J, is modulated by a carbon-carbon double bond. However, the efficacy of the carbon-carbon double bond as an exchange coupler is determined by the molecular conformation. Our results show that the exchange parameters correlate with phenyl-ring torsion angles (phi) via a simple Karplus-Conroy-type relation: J = 44 cos(2) phi - 17. Comparison of these results to those obtained for our isostructural series of bis(semiquinone) biradicals shows that both the magnitude of J and the resistance of ferromagnetic J to bond torsions is proportional to the spin density adjacent to the exchange coupler.