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

Abstract

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.

Hierarchical Uniform Supramolecular Conjugated Spherulites with Suppression of Defect Emission

“…In this study, we established a molecular design principle of supramolecular conjugated macromolecules with orthogonal hydrogen-bonding interactions to enable a secondary planar conformation toward controlling and improving photonic behavior, defined as supramolecular plastic photonics (SPPs: photonic behavior of polymeric system can be significantly improved by supramolecular approach). This oriented planar conformation self-organizes into ordered tertiary microstructure supramolecular spherulites in accordance with the synergistically molecular attractor-repulsor theory (Scheme 1, Figures 1A and 1B) (Li et al., 2018, Wang et al., 2018, Xu et al., 2018). A hierarchical supramolecular artificial architecture with a series of multidimensional orthogonal hydrogen bonds in rigid crystalline framework is obtained from our bulky supramolecular spiro-terfluorene, 2,7-bis(3′,6′-bis(octyloxy)spiro[fluorene-9,9′-xanthen]-2-yl)spiro[fluorene-9,9′-thioxanthene]-10′,10′-dioxide (DOSFX-SFXSO).…”

Ultrastable Supramolecular Self‐Encapsulated Wide‐Bandgap Conjugated Polymers for Large‐Area and Flexible Electroluminescent Devices

“…Inspired by the supramolecular steric hindrance (SSH) effect of bulk units on molecular conformation and packing, we proposed a novel strategy based on the molecular integration of steric bulk groups and supramolecular synthons into one functional molecule or chain (Scheme A) . For all the effort put into the design of polyfluorenes over the last few decades, the utilization of the fluorene 4,5 position has been completely ignored.…”

“…For all the effort put into the design of polyfluorenes over the last few decades, the utilization of the fluorene 4,5 position has been completely ignored. Recently, the second planar (β) conformational stable polydiarylfluorenes was designed with a balance between the steric interaction of bulky diphenyl (9‐position) and the entangled attraction of octyl side chain at 4‐position (van der Waals force, vDW) . Herein, we demonstrate a supramolecular approach in plastic electronic (also called supramolecular plastic electronic, SPE) to subtly avoid various pathways for defect generation based on ketone and aggregate formation to construct supramolecular self‐encapsulated polyfluorenes.…”

An Overview of Molecular Packing Mode in Two‐Dimensional Organic Nanomaterials via Supramolecular Assembly

“…As an important supplement of non-planar molecular system, Xie and his group designed a typical attractor-repulsor molecule N,N-diphenyl-4-(9-phenyl-uoren-9-yl) phenylamine (TPA-PF) to investigate the supramolecular steric hindrance (SSH) effect on the 2D self-assembly behavior of organic nanostructures. [65] 2D truncated nanosheets are observed ( Figure 5d) after reprecipitation in solution. As a repeat unit, three TPA-PF molecules are connected with each other by C-H•••π interactions in an interdigital lipid bilayerlike interlayer stacking (Figure 5e).…”

“…f) Molecular arrangement of TPA-PF viewed from c and b axis of the crystal lattice, respectively. Reproduced with permission from Ref [65]…”