Disentangling different modes of mobility for triphenylphosphine oxide adsorbed on alumina

Triphenylphosphine oxide (TPPO, 1) has been adsorbed on neutral alumina by dry grinding of the components in the absence of a solvent. The adsorption proves translational mobility of 1 on the surface of alumina. Different surface coverages from a densely packed monolayer (99% coverage) to a dilute sub-monolayer (25%) have been produced. The samples have been studied by diverse multinuclear ¹H, ¹³C, and ³¹P variable temperature solid-state nuclear magnetic resonance (NMR) techniques. The interactions of 1 with the surface are determined by hydrogen bonding of the P=O group to OH groups on the surface. The ³¹P solid-state NMR spectra prove that even at low temperatures, the molecules of 1 are highly mobile on the surface. Using T₁ and T₂ relaxation time analyses of the ³¹P resonance in the solid state at variable temperatures allowed the identification and quantification of two different modes of mobility. Besides the translational mobility that consists of jumps from one hydrogen-bonding OH site on the surface to an adjacent one, a rotational movement around the axis defined by the P=O group of 1 occurs.