Ionic self-assembled derivatives of perylenetetracarboxylic dianhydride: facile synthesis, morphology and structures

Abstract

A facile ionic self-assembly method was used to synthesize technologically important derivatives of perylenetetracarboxylic dianhydride (PTCDA). This extremely facile one-pot synthesis was performed in water and provided relatively pure complexes precipitated from water in high yield at room temperature. This is particularly interesting because the synthesis of most PTCDA derivatives using conventional methods often requires relatively complicated and harsh conditions. The self-assembly of the complexes was studied under different conditions. In ethanol–water or toluene–acetone binary solvents, long aggregates in the range of micrometers were obtained. Through a slow evaporation of toluene, one of the complexes can form ultralong aggregates, up to ∼4 mm in length. The structural packing of these systems is dominated by the stacking of the rigid perylene disks, embedded in an aliphatic soft matrix that may or may not crystallize, as evidenced by X-ray diffraction (XRD). Details of the structural packing such as layer spacings and perylene tilts also determine different fluorescence functionalities.