NITROXYLS AND PELDOR: NITROXYL RADICALS IN PULSED ELECTRON-ELECTRON DOUBLE RESONANCE SPECTROSCOPY

摘要

The review considers the main propositions of PELDOR theory. It is shown how from the analysis of PELDOR time traces it is possible to find the parameters of a spin system such as the distance and the distance distribution (spectrum), number of spins in aggregates and complexes, exchange integral and how to separate for the following analysis the inter- and intramolecular contributions to the general dipole interaction. Examples of PELDOR application in the studies of the spatial distribution of nitroxyl radicals, the charge effect of dipolar interacting nitroxyls on their spatial distribution are given and the results of the determination of distances and the spectrum of distances for nitroxyl bi-, tri-, and tetraradicals are presented. The works on nitroxyl radicals in which the orientation selectivity effect, spin exchange, and conformational properties of the radicals are examined by the PELDOR method are analyzed. The studies of the structure of paramagnetic ion–nitroxyl radical pairs and the PELDOR data on nitroxyls at high frequencies (high fields) are considered. The last section of the review is devoted to the works examining the properties such as the molecular flexibility of oligomers and supramolecules contains nitroxyl radicals.