Rylene Diimides Featuring Quadruple C─H···(O═C) Locking for High‐Mobility Organic Semiconductors

ABSTRACT Polycyclic aromatic hydrocarbons with large conjugated planes and low reorganization energy serve as an ideal molecular platform for organic semiconductors; however, precisely controlling their aggregated structures to achieve large transfer integrals and thus excellent charge transport efficiency remains a significant challenge. Herein, we design and synthesize a sila‐annulated hexarylene diimide ( 2Si‐HDI ) featuring imide units at both peri ‐positions and two silole rings at the central bay ‐positions. Through the quadruple C─H···(O═C) locking between carbonyls of the diimide groups and the hydrogen atoms of the 1,1'‐diethylsilyl groups at the silole rings, we realized the first 1D slipped π – π stacking of ultra‐long rylenes (naphthalene unit ≥ 6), providing groundbreaking guidance for the well‐ordered π – π self‐assembly of large planar PAHs relevant to armchair graphene nanoribbons. The single‐crystalline organic field‐effect transistor properties of 2Si‐HDI exhibit hole/electron mobilities up to 3.08/0.06 cm 2 V −1 s −1 . Theoretical calculations reveal hole/electron transfer integrals of 2Si‐HDI as high as 110.08/78.08 meV along the π – π stacking direction, rationalizing its superior charge transport performance.