Chemistry of Anthracene–Acetylene Oligomers XXV: On‐Surface Chirality of a Self‐Assembled Molecular Network of a Fan‐Blade‐Shaped Anthracene–Acetylene Macrocycle with a Long Alkyl Chain

Abstract

An anthracene cyclic dimer with two different linkers and a dodecyl group was synthesized by means of coupling reactions. The calculated structure had a planar macrocyclic π core and a linear alkyl chain. Scanning tunneling microscopy observations at the 1-phenyloctane/graphite interface revealed that the molecules formed a self-assembled monolayer that consisted of linear striped bright and dark bands. In each domain, the molecular network consisted of either Re or Si molecules that differed in the two-dimensional chirality about the macrocyclic faces, which led to a unique conglomerate-type self-assembly. The molecular packing mode and the conformation of the alkyl chains are discussed in terms of the intermolecular interactions and the interactions between the molecules and the graphite surface with the aid of MM3 simulations of a model system.

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

“…Fan-blade-shaped macrocycle 188 with ad odecyl group could form as elf-assembled network on graphite. [308] All molecules in each domain of self-assembly have the same two-dimensionalc hirality.At heoretical calculation of cyclotrimer 189 suggested as malle nergy difference (0.5 kJ mol À1 )b etween the C 2 -a nd C s -symmetric struc- tures. The C 2 -symmetric structurei nt he solid state wasd etermined by X-ray crystallographic analysis (CCDC:6 11249).…”

“…The selected examples of strained macrocycles are depicted in Figure . Fan‐blade‐shaped macrocycle 187 was synthesized as a racemic mixture by Eglinton coupling . The pure enantiomer could be resolved by using chiral high‐performance liquid chromatography.…”

“…The free energy of activation Δ G ≠ for enantiomerization is estimated to be 122 kJ mol −1 by kinetic analysis. Fan‐blade‐shaped macrocycle 188 with a dodecyl group could form a self‐assembled network on graphite . All molecules in each domain of self‐assembly have the same two‐dimensional chirality.…”

“…Fan-blade-shaped macrocycle 187 was synthesized as ar acemic mixture by Eglinton coupling. [305][306][307][308] The pure enantiomer could be resolved by using chiral high-performance liquid chromatography. DFT calculations pointed out that the macrocyclic structure is slightly distorted because of the stericr epulsion between ah ydrogen atom and am ethoxy group inside the macrocyclic ring.…”

Planar Anthracene–Acetylene Frameworks as a Stereogenic Motif

“…(b) An enlarged image (unit cell parameters: a= 1.1 Å, b= 1.1 Å, γ =80°, Z= 2) and molecular models superimposed on the image (Ref. , with permission). The white arrows in (b) indicate the directions of the main symmetric axes of underlying highly ordered pyrolytic graphite.…”