Dynamics of 9-hydroxyphenalenone studied by one-dimensional solid-state spin exchange NMR

We present a new NMR method to clarify the dynamics of proton tautomerism in solid 9-hydroxyphenalenone. Two 13C resonance lines influenced by the proton tautomerism have a chemical-shift difference between them, which increases with decreasing temperature. To depict the precise potential curve of the proton tautomerism, the chemical-shift difference when the proton tautomerism is completely frozen is necessary. For solid 9-hydroxyphenalenone and its derivatives, the freezing temperatures are often under -100 degrees C. When the freezing temperatures are below the temperature range in which standard magic angle spinning NMR probes can perform a sample spinning, it is very difficult to obtain the shift difference. The NMR experiments based on this new method are performed at a temperature significantly higher than -100 degrees C at which the proton tautomerism is still active. The new method yields the 13C spin relaxation rates, the rates for the proton tautomerism, and the populations of the two tautomers. Using the populations and the 13C chemical-shift difference at that temperature, we determined the chemical-shift difference at the freezing temperature. We also obtained several parameters characterizing the potential profile for the proton dynamics in solid 9-hydroxyphenalenone.