Capturing the Interplay Between TADF and RTP Through Mechanically Flexible Polymorphic Optical Waveguides

Abstract

Polymorphism plays a pivotal role in generating a range of crystalline materials with diverse photophysical and mechanical attributes, all originating from the same molecule. Here, we showcase two distinct polymorphs: green (GY) emissive and orange (OR) emissive crystals of 5'‐(4‐(diphenylamino)phenyl)‐[2,2'‐bithiophene]‐5‐carbaldehyde (TPA‐CHO). These polymorphs display differing optical characteristics, with GY exhibiting thermally activated delayed fluorescence (TADF) and OR showing room temperature phosphorescence (RTP). Additionally, both polymorphic crystals display mechanical flexibility and optical waveguiding capabilities. Leveraging the AFM‐tip‐based mechanophotonics technique, we position the GY optical waveguide at varying lengths perpendicular to the OR waveguide. This approach facilitates the exploration of the interplay between TADF and RTP phenomena by judiciously controlling the optical path length of crystal waveguides. Essentially, our approach provides a clear pathway for understanding and controlling the photophysical processes in organic molecular crystals, paving the way for advancements in polymorphic crystal‐based photonic circuit technologies.