Methyl reorientation in solid 3-ethylchrysene and 3-isopropylchrysene

Abstract

We have measured the proton spin-lattice relaxation rate as a function of temperature in polycrystalline 3-ethylchrysene at nuclear magnetic resonance Larmor frequencies of 53.0 and 22.5 MHz and in polycrystalline 3-isopropylchrysene at 53.0, 22.5 and 8.50 MHz. The syntheses of these new compounds are presented. The relatively large chrysene backbone creates an ideal and unique environment for the alkyl groups such that methyl group rotation is the only motion on the nuclear magnetic resonance Larmor frequency timescale over a large temperature range. The relaxation rate data are interpreted in terms of the simplest possible dynamical model; that of random hopping for the methyl group(s), all of which are equivalent in the solid state. The barriers of 11–12 kJ mol −1 are typical for methyl groups in `isolated' ethyl and isopropyl groups.