Organic polymorphs based on an AEE-active tetraphenylethene salicylaldehyde Schiff-base derivative: the effect of molecular conformation on luminescence properties

Abstract

An aggregation-enhanced emission (AEE)-active tetraphenylethene salicylaldehyde Schiff-base derivative, TPE-Nap, was prepared using a facile synthesis. The AEE property of TPE-Nap was studied by luminescence and absorption spectra, and was attributed to the CN isomerization restriction and the excited-state intramolecular proton transfer (ESIPT) process. Polymorphs TPE-Nap-Y and TPE-Nap-O were prepared from TPE-Nap, and their emission color and intensity were compared. TPE-Nap-Y is a yellow block crystal with a very weak yellow emission, with its main peak at 565 nm, while TPE-Nap-O is an orange plate crystal that gave a stronger orange emission, with its main peak at 583 nm. Single crystal diffraction data were used to demonstrate the structure–property relationship. The most unique feature was that the torsion angle of TPE-Nap-Y between the benzene ring of the TPE unit and the Nap unit was 54.08°, while that of TPE-Nap-O was 14.19°. Interestingly, the TPE unit assumed propeller-like nonplanar conformations that likely led to different intermolecular interactions, such as C–H⋯O interactions (2.529 Å and 2.617 Å) in TPE-Nap-O and C–H⋯π interactions (3.224 Å and 3.791 Å) in TPE-Nap-Y. These were influenced by the torsion angle, although the molecules in both crystals were arranged in a similar end-to-end slip-stacking mode. These results inferred that the molecular conformation was evidently affected by luminescent properties. Crystals possessing a slightly twisted molecular conformation exhibited stronger emission than those possessing a heavily twisted molecular conformation. These investigations will expand the research on the relationship between the molecular conformation and the emission properties of organic solids, and might provide a new development strategy for organic polymorphs.