Controllable Fabrication of Organic Cocrystals with Interior Hollow Structure Based on Donor-Acceptor Charge Transfer Molecules

Fluorescent hollow organic molecular cocrystals comprised of (E)-4-(2(anthracen-9-yl)vinyl)pyridine-1,2,4,5-tetracyanobenzene (APE-TCNB) were prepared via a surfactant-mediated co-precipitation method. The size and morphology of these cocrystals could be easily tuned by varying the type and concentration of the surfactant, incubation time, and temperature. Moreover, optical fluorescence and scanning electron microscopy characterization indicated that the APE-TCNB microcrystals contained two symmetric empty cavities when 3-(N, N-dimethyldodecylammonio)propane sulfonate (BS12) was used as the surfactant. The cross-polarized microscope and powder X-ray diffraction (PXRD) measurements both showed that the prepared microcrystals exhibited high crystallinity. APE and TCNB molecules were found to align parallelly along the crystallographic a-axis in the crystal lattice, and the strong pi-pi intermolecular interactions facilitated the formation of unique crystal chambers. A series of measurements and characterization, including UV-Vis absorption spectroscopy, infrared spectroscopy, steady-state, and time-resolved fluorescence spectroscopy, also verified that strong charge-transfer (CT) interactions had been established in the APE-TCNB microcrystals. Moreover, these APE-TCNB microcrystals could emit bright red luminescence, which extended to the near-infrared region (similar to 800 nm), displaying a strong charge-transfer property. Here, we have shown a general facile way to make organic cocrystals with complex structures and topologies using a self-assembly method.

Automated summary

In this study, fluorescent hollow organic molecular cocrystals were prepared using a surfactant-mediated co-precipitation method. The size and morphology of the cocrystals could be easily controlled by adjusting the surfactant type, concentration, incubation time, and temperature. The cocrystals exhibited high crystallinity and contained two symmetric empty cavities when a specific surfactant was used. Additionally, the cocrystals emitted bright red luminescence with a strong charge-transfer property.