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

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 cm² 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 cm² 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.