Methyl and t-butyl reorientation in an organic molecular solid

We have determined the molecular and crystal structure of 4,5-dibromo-2,7-di-t-butyl-9,9-dimethylxanthene and measured the 1H spin-lattice relaxation rate from 87 to 270 K at NMR frequencies of ω/2π=8.50, 22.5, and 53.0 MHz. All molecules in the crystal see the same intra and intermolecular environment and the repeating unit is half a molecule. We have extended models developed for 1H spin-lattice relaxation resulting from the reorientation of a t-butyl group and its constituent methyl groups to include these rotors and the 9-methyl groups. The relaxation rate data is well-fitted assuming that the t-butyl groups and all three of their constituent methyl groups, as well as the 9-methyl groups all reorient with an NMR activation energy of 15.8±1.6 kJ mol−1 corresponding to a barrier of 17.4±3.2 kJ mol−1. Only intramethyl and intra-t-butyl intermethyl spin-spin interactions need be considered. A unique random-motion Debye (or BPP) spectral density will not fit the data for any reasonable choice of parameters. A distribution of activation energies is required.