Benzocarbazole anions intercalated layered double hydroxide and its tunable fluorescence

Abstract

Luminescent benzocarbazole anions (BCZC) intercalated into the interlayer region of Mg–Al-layered double hydroxides (BCZC/LDH) with different layered charge densities (LCD) were prepared. The structure and chemical composition of the composites were characterized by X-ray diffraction, elemental analysis, thermogravimetry and differential thermal analysis (TG-DTA), infrared spectra (FT-IR), UV-vis absorption and fluorescence spectroscopy. The photoemission behavior of BCZC in the LDH matrix with high (Mg/Al ratio = 1.801) and low (Mg/Al ratio = 3.132) LCD is similar to that of BCZC solid and aqueous solution states respectively, indicating that the luminescence performances of the intercalated dye anions can be tuned by adjusting the LCD of the LDH layer. Moreover, the thermal stability and stacking order of BCZC are largely improved upon intercalation, and the BCZC/LDH thin film exhibits well polarized luminescence with the luminescent anisotropy of 0.15–0.20. In addition, molecular dynamics (MD) simulation was employed to calculate the basal spacing and molecular arrangement of the intercalated BCZC within the LDH matrix. The simulation results show that the distribution of BCZC anions is much broader in the gallery of Mg–Al-LDH with high LCD, while BCZC anions exhibit a more ordered arrangement in LDH with low LCD. Furthermore, the radial distribution functions of interlayer water molecules were also studied. Based on the combination of experiment and theoretical simulation, this work provides a detailed understanding of the tunable photoluminescence, orientation and diffusion behavior of the luminescent molecules confined within the gallery of a 2D inorganic matrix.