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

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 C[double bond, length as m-dash]N 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.