Phenyl Derivatives Modulate the Luminescent Properties and Stability of CzBTM-Type Radicals.

The distinctive electron structures of luminescent radicals offer considerable potential for a diverse array of applications. Up to now, the luminescent properties of radicals have been modulated through the introduction of electron-donating substituents, predominantly derivatives of carbazole and polyaromatic amines with more and more complicated structures and redshifted luminescent spectra. Herein, four kinds of ( N -carbazolyl)bis(2,4,6-tirchlorophenyl)-methyl (CzBTM) radicals, Ph 2 CzBTM , Mes 2 CzBTM , Ph 2 PyIDBTM , and Mes 2 PyIDBTM , were synthesized and characterized by introducing simple phenyl and 2,4,6-trimethylphenyl groups to CzBTM and PyIDBTM. These radicals exhibit rare blueshifted emission spectra compared to their parent radicals. Furthermore, modifications to CzBTM significantly enhanced the photoluminescence quantum yields (PLQYs), with a highest PLQY of 21% for Mes 2 CzBTM among CzBTM-type radicals. Additionally, the molecular structures, photophysical properties of molecular orbitals, and stability of the four radicals were systematically investigated. This study provides a novel strategy for tuning the luminescent color of radicals to shorter wavelengths and improving thermostability.