Modulated Luminescence of a Stable Open-Shell Triarylmethyl Radical: Effects of Chemical Modification on Its Electronic Structure and Physical Properties.

The open-shell luminescent (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl (PyBTM) radical contains a nitrogen atom that behaves as a stimulus-responsive site. Chemical modification at this nitrogen atom, such as coordination of B(C F ) or methylation, shifts the emission maximum to the low-energy region and increases the reduction potential. The emission colour may be regulated by the reversible Lewis acid-base reaction between B(C F ) and PyBTM. Comparison of the optical and electrochemical properties of the radicals with the electronic structures calculated by density functional theory has indicated that the chemical modification decreased the energy level of the β-singly occupied molecular orbital, a key orbital in determining the optical and electrochemical properties of such systems.