RESUMEN
Phosphorescent materials with time-dependent phosphorescence colors (TDPCs) have great potential in advanced optical applications. Synthesis of such materials is attractive but challenging. Here, a series of carbon dot-porous Al2 O3 composites exhibiting distinctive TDPC characteristics is prepared by high-temperature pyrolysis of Al-based metal-organic frameworks NH2 -MIL-101(Al). The composite synthesized at 700 °C (CDs@Al2 O3 -700) shows an obvious change in phosphorescence color from blue to green after removing the excitation light of 280 nm. Photophysical analysis reveals that two emission centers in CDs, namely carbon core and surface states, are responsible for the short-lived blue phosphorescence (96 ms) and long-lived green phosphorescence (911 ms), respectively. The combination of blue and green phosphorescence with different decay rates triggering the interesting TDPC phenomenon. CDs@Al2 O3 -700 has a significantly high phosphorescence quantum yield of up to 41.7% and possesses an excellent optical stability against water, organic solvents, and strong oxidants, which benefits from the multi-confinement of CDs by the porous Al2 O3 matrix through rigid network, strong space constraint, and stable covalent bonding. Based on the TDPC property, multilevel coding patterns composed of CDs@Al2 O3 are successfully fabricated for advanced dynamic information encryption.
RESUMEN
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.
RESUMEN
Developing afterglow materials with wide-range and time-dependent colors is highly desirable but challenging. Herein, by calcinating the mixture of Rhodamine B and NH4Al(OH)2CO3, carbon dots (CDs) are generated and in situ embedded in the porous Al2O3, forming the CDs@Al2O3 composite, which exhibits time-dependent phosphorescence colors (TDPCs) from blue to green after excited by a UV lamp. Photophysical studies reveal that the blue phosphorescence with a short lifetime of 214 ms originates from the carbon core state, while the green phosphorescence with a long lifetime of 915 ms is associated with the surface state of CDs. Simultaneous activation of the blue and green phosphorescence with different lifetimes induces the TDPC performance. Using CDs@Al2O3 as the donor, a series of long-wavelength fluorescent dyes including Rhodamine 123, Rhodamine 6G, and Rhodamine B as the acceptors, and epoxy resin (ER) as the matrix, a dual-phosphorescence resonance energy transfer system (CDs@Al2O3-dye-ER) is constructed to rationally regulate the afterglow emission, conferring the full-color dynamic afterglow from blue to red at different decay times with high afterglow quantum yields of up to 48.2%. The fascinating afterglow properties of the CDs@Al2O3-dye-ER composites enable their successful applications in multidimensional information encryption and polychrome 3D artworks.