Optical Nature of Non-Substituted Triphenylmethyl Cation: Crystalline State Emission, Thermochromism, and Phosphorescence

Since the discovery of the triphenylmethyl (trityl) cation 120 years ago, a variety of aromatic cations having various colors and luminescence properties have been rigorously studied. Many, differently substituted trityl cations have been synthesized and their optical properties have been elucidated. However, the optical properties of the parent, non-substituted and highly reactive trityl cation, which was observed to be very weakly luminescent, have not been subjected to detailed investigation. In the effort described herein, we explored the optical nature of non-substituted trityl hexafluorophosphate (PF6) in the crystalline state. Trityl PF6 was found to exist as two crystal polymorphs including a yellow (Y) and an orange (O) form. Moreover, we observed that these crystalline forms display crystalline-state emission with different colors. The results of X-ray crystallographic analysis showed that the two polymorphs have totally different molecular packing arrangements. Furthermore, an investigation of their optical properties revealed that the O-crystal undergoes a distinct color change to yellow upon cooling as a consequence of a change in the nature of the charge transfer interaction between the cation and PF6 anion, and that both the Y and O crystal exhibit phosphorescence.