Contrasting Mechanochromic Luminescence of Enantiopure and Racemic Pyrenylprolinamides: Elucidating Solid-State Excimer Orientation by Circularly Polarized Luminescence

Circularly polarized luminescence (CPL) and mechanochromic luminescence (MCL) have independently made substantial progress in recent years. However, the exploration of MCL in solid-state CPL materials, which holds practical significance, is still in its infancy. Herein, we report the MCL properties of readily accessible chiral pyrenylprolinamides bearing tert-butoxycarbonyl (Boc) or 2,2,2-trichloroethoxycarbonyl (Troc) groups. Enantiopure crystals of the Boc derivative display a greater MCL wavelength shift than racemic crystals, while the Troc derivative exhibit the opposite trend. Most notably, the enantiopure crystals show mechanochromic CPL. Unlike in previous examples, where CPL is quenched upon amorphization, robust CPL spectra were observed even in the amorphous states. By applying the excimer chirality rule, we have, for the first time, acquired insights into the excited-state structures within mechanically generated amorphous states. These findings offer a novel design strategy for developing mechanochromic CPL materials, paving the way for the future advancements in this emerging field.