Journal of Physical Chemistry, Vol.100, No.32, 13428-13432, 1996
Determination of End-to-End Distances in Oligomers by Pulsed EPR
Conformations of end-labeled alkanes in a rigid polymer matrix were investigated using the pulsed double electron-electron resonance (DEER) method. To this end, dipolar spectra of a series of aliphatic dicarbonic acids with 8-20 methylene units and chain ends bifunctionalized with nitroxide radicals were recorded in a polystyrene matrix. The biradicals are derived from hindered amine light stabilizers (HALS), used as polymer additives. Analysis of the dipolar spectra allows the determination of the end-to-end distances of the oligomer biradicals. The experiments show that the "flexible" alkane chains are almost completely stretched. This observation is consistent with the results of force field calculations.
Keywords:SPIN ECHO METHOD;GLASSY POLYCARBONATE;LOCAL PACKING;RESONANCE;NMR;SPECTROSCOPY;SOLIDS;PAIRS