SMART Design of a Bulk-Capped Supramolecular Segment for the Assembly into Organic Interdigital Lipid Bilayer-Like (ILB) Nanosheets

Rational molecular design for the organic nanocrystal morphology still remains a challenge due to the structural diversity and complicated weak intermolecular interactions. In this work, a typical attractor–repulsor molecule N,N-diphenyl-4-(9-phenyl-fluoren-9-yl) phenylamine (TPA-PF) is designed to explore a general assembly strategy for 2D nanocrystals. Via an interdigital lipid bilayer-like (ILB) molecular packing mode, large-sized lamellar 2D nanosheets are obtained with a length:width:thickness ratio as ≈2500:1000:1. The d-spacing of the largest (001) plane is 1.32 nm, which equals to the thickness of a single interdigital stacking layer. The synergetic effect of the attractive supramolecular segment (TPA) and the repulsive bulky group (PF) is supposed to be the critical factor for the ILB packing that leads to the 2D structures. The attractor–repulsor molecule design is expected to be an effective strategy for the growth of 2D nanocrystals based on small organic molecules.