A combined study based on experiment and molecular dynamics: perylene tetracarboxylate intercalated in a layered...

This paper describes a combined experimental and theoretical simulation investigation on the photophysical properties, thermolysis, and orientation of 3,4,9,10-perylene tetracarboxylate (PTCB) intercalated Mg-Al-layered double hydroxide (PTCB/Mg-Al-LDH). UV-vis absorption and fluorescence spectroscopy show the existence of PTCB aggregates within the gallery of LDH, indicative of H-type (blue-shifted absorption band) and J-type dimers (red-shifted absorption band). In situ high-temperature X-ray diffraction (HT-XRD), thermogravimetry and differential thermal analysis (TG-DTA) and elemental analysis were used to study the thermal decomposition properties of PTCB/Mg-Al-LDH, and it was found that the decomposition temperature of the intercalated PTCB is lower than its pristine form (460 vs 565 degrees C), indicating that the strong pi-pi interaction among PTCB was weakened by the positively charged LDH host layers. Molecular dynamics (MD) calculations were employed to simulate the molecular arrangement and aggregation behavior of intercalated PTCB in the gallery of Mg-Al-LDH. The simulation results show that the intercalated PTCB anions exhibit a tendency from tilted to vertical orientation with respect to the layers as the interlayer water content increases, furthermore, the H and J-type dimer species are most likely populated under low and high hydration conditions, respectively. Moreover, the distribution of interlayer water molecules are also discussed.