Proton Spin-Lattice Relaxation in Organic Molecular Solids: Polymorphism and the Dependence on Sample Preparation

We report solid-state nuclear magnetic resonance ¹ H spin-lattice relaxation, single-crystal X-ray diffraction, powder X-ray diffraction, field emission scanning electron microscopy, and differential scanning calorimetry in solid samples of 2-ethylanthracene (EA) and 2-ethylanthraquinone (EAQ) that have been physically purified in different ways from the same commercial starting compounds. The solid-state ¹ H spin-lattice relaxation is always non-exponential at high temperatures as expected when CH₃ rotation is responsible for the relaxation. The ¹ H spin-lattice relaxation experiments are very sensitive to the "several-molecule" (clusters) structure of these van der Waals molecular solids. In the three differently prepared samples of EAQ, the relaxation also becomes very non-exponential at low temperatures. This is very unusual and the decay of the nuclear magnetization can be fitted with both a stretched exponential and a double exponential. This unusual result correlates with the powder X-ray diffractometry results and suggests that the anomalous relaxation is due to crystallites of two (or more) different polymorphs (concomitant polymorphism).