Self‐Assembly of Bowl‐Shaped Naphthalimide‐Annulated Corannulene

Abstract

The self‐assembly of a bowl‐shaped naphthalimide‐annulated corannulene of high solubility has been studied in a variety of solvents by NMR and UV/Vis spectroscopy. Evaluation by the anti‐cooperative K2‐K model revealed the formation of supramolecular dimers of outstanding thermodynamic stability. Further structural proof for the almost exclusive formation of dimers over extended aggregates is demonstrated by atomic force microscopy (AFM) and diffusion ordered spectroscopy (DOSY) measurements as well as by theoretical calculations. Thus, herein we present the first report of a supramolecular dimer of an annulated corannulene derivative in solution and discuss its extraordinarily high thermodynamic stability with association constants up to >106 M−1 in methylcyclohexane, which is comparable to the association constants given for planar phthalocyanine and perylene bisimide dyes.

Shape-assisted self-assembly

“…Flat molecules (zero curvature) are frequently observed in supramolecular polymerizations due to ease of access to these structures synthetically [32][33][34] . Bowl shapes (positive) 35,36 , and more so saddles (negative) 28,37,38 , are far less commonly used topographies for the opposite reason. Yet, to introduce order in an assembly, negatively curved systems stand out as preferred candidates to induce eclipsed stacking because transverse rigidity is increased on both molecular and macroscopic scales 27,28,39 .…”

Porphyrin–Ryleneimide Hybrids: Tuning of Visible and Near-Infrared Absorption by Chromophore Desymmetrization

“… 7 − 9 Hybridization of ryleneimides with nonbenzenoid and heterocyclic moieties provides a versatile though still relatively unexplored route to structurally unique functional dyes. In one general strategy, 9 , 10 tandem Pd-catalyzed couplings have been used for synthesis of ryleneimide-fused indenes, 11 azulenes, 12 corannulenes, 13 , 14 and heteroaromatics. 15 Our group has employed naphthaleneimide-fused pyrrole building blocks 16 for modular synthesis of electron-deficient porphyrins, 16 azacoronenes, 17 − 19 bipyrroles, 20 and polymers.…”

“…Ryleneimides, most notably perylenediimides (PDIs), are one of the most important classes of organic dyes, with an exceptional scope of industrial and research applications. − Their electronic and self-assembly properties can be tuned by homologation of the rylene backbone, modification of imide functionalities, peripheral substitution, and ring fusion. − Hybridization of ryleneimides with nonbenzenoid and heterocyclic moieties provides a versatile though still relatively unexplored route to structurally unique functional dyes. In one general strategy, , tandem Pd-catalyzed couplings have been used for synthesis of ryleneimide-fused indenes, azulenes, corannulenes, , and heteroaromatics . Our group has employed naphthaleneimide-fused pyrrole building blocks for modular synthesis of electron-deficient porphyrins, azacoronenes, − bipyrroles, and polymers .…”

Shape-Assisted Self-Assembly

“…Flat molecules are frequently observed in supramolecular polymerizations due to ease of access to these structures synthetically (8,27,28). Bowl shapes (29,30), and more so saddles (24,31,32), are far less commonly used topographies for the opposite reason. Yet, to introduce order in an assembly, negatively curved systems stand out as preferred candidates to induce eclipsed stacking because transverse rigidity is increased on both molecular and macroscopic scales (23,24,33).…”