Calcination-Controlled Synthesis of Carbon Dots@MgF₂ Composites with Yellow, White, and Ultraviolet-Blue Thermally...

It is attractive but challenging to develop carbon dot (CD) based materials with tunable thermally activated delayed fluorescence (TADF), especially in the long wavelength region. Here, by simply calcinating the mixture of m-phenylenediamine and MgF₂ at 300-500 °C, a series of CDs@MgF₂ composites exhibiting yellow, white, and ultraviolet-blue TADF with high photoluminescence quantum yields of up to 37.6% are prepared. Photophysical studies reveal that the yellow TADF with long lifetimes of 810-1106 ms originates from the surface emission centers of CDs, while the ultraviolet-blue TADF with short lifetimes of 266-379 ms is related to the carbon core emission centers. The combination of yellow and ultraviolet-blue TADF in a single material triggers dynamic afterglow with time-dependent colors from white to yellow. The MgF₂ matrix offers multiple confinement of CDs through a rigid network, strong space constraint, and robust covalent/hydrogen bonding, thus preventing the triplet excitations from non-radiative transitions. The electron-withdrawing fluorine atoms induce substantial spin-orbit coupling and reduce the singlet-triplet energy gap, consequently facilitating the reverse intersystem crossing to enhance TADF efficiency. Importantly, the CDs@MgF₂ composites possess outstanding optical stability against water, organic solvents, strong acids, bases, and oxidants. The fascinating TADF features enable the successful demonstration of multilevel information encryption using CDs@MgF₂.