Integrating Strong Luminescence and High Mobility in Organic Single Crystals of Covalent Pyrene Dimers

Abstract Simultaneously achieving strong luminescence and high mobility in organic semiconductors remains a challenge. Herein, two covalently dimerized pyrene derivatives (1Py‐2Py and 1Py‐1Py) with distinct chemical linkages and crystal packing arrangements are presented. Remarkably, the radiative transition of pyrene is gradually unforbidden from 1Py‐2Py to 1Py‐1Py. Moreover, 1Py‐2Py showcases 1D long‐range π─π stacking, while 1Py‐1Py exhibits 2D herringbone packing formed by a vast network of intermolecular C─H∙∙∙π interactions. To the surprise, both high photoluminescence quantum yield (PLQY = 72.17%) and high hole mobility ( µ = 32.6 cm 2 V −1 s −1 ) are simultaneously harvested in 1Py‐1Py crystal, which are far superior to those in 1Py‐2Py crystal (PLQY = 48.66% and µ = 0.05 cm 2 V −1 s −1 ). These findings underscore the potential of covalent pyrene dimer with 1‐position linkages as a promising organic semiconductor for the exceptional combination of strong luminescence and high mobility, which is substantially ascribed to the efficiently unforbidden emission and the favorable 2D charge transport pathways.