Structure and molecular dynamics of host–guest complexes of TEMPO with cucurbituryl: An ESR and DFT study

Abstract

Host–guest complexes are of interest as promising nanodevices for molecular recognition and chemosensors. In this work, the structure and molecular dynamics of complexes of the nitroxyl radical TEMPO (I), as models of indicator and analyte, with cucurbituril CB[7] in solution and in the solid phase have been studied by ESR and DFT methods. The kinetic accessibility of the NO group of I for water-soluble reagents has been determined. By simulation of the ESR spectra of the complex, the rotational diffusion coefficients and the anisotropy of its rotation have been determined. To study the rotational mobility of the guest in the CB[7] cavity, solid solutions of I@CB[7] in the CB[7] matrix have been obtained. The ESR spectra indicate rapid jump-like rotation of I about an axis oriented along the normal to the CB[7] portals. The formation energy and the spatial structure of the complex have been calculated by the DFT method; a change in the spin density on the NO group with changing the orientation of I in the CB[7] cavity has been found.