Synthesis and Properties of a Cyclohexa‐2,7‐anthrylene Ethynylene Derivative

Abstract

The synthesis of a cyclohexa‐2,7‐(4,5‐diaryl)anthrylene ethynylene (1) was achieved for the first time by using 1,8‐diaryl‐3,6‐diborylanthracene and 1,8‐diaryl‐3,6‐diiodoanthracene as key synthetic intermediates. Macrocycle 1 possesses a planar conformation of approximately D6h symmetry, because of the triple‐bond linker between the anthracene units at the 2,7‐positions. It was confirmed that macrocycle 1, bearing bulky substituents at the outer peripheral positions, behaves as a monomeric form in solution without π‐stacking self‐association. Macrocycle 1 has an inner‐cavity size that allows specific inclusion of [9]cycloparaphenylene ([9]CPP), but not [8]CPP or [10]CPP, through an aromatic edge‐to‐face CH‐π interaction.

Structures and Supramolecular Properties of Inclusion Complexes of Anthracene‐Triptycene Nanocages with Fullerene Guests and Their Dynamic Motion as Molecular Gyroscopes

“…Target cages 3 were synthesized via an improved route, as shown in Scheme 1. In order to apply the regioselective Hartwig‐Miyaura borylation reported by Kobayashi et al., [7] we chose 1,8‐diphenylanthracene derivatives 5 with 2,4,6‐trimethylphenyl (mesityl : Mes), pentafluorophenyl (C 6 F 5 ), and 2,4,6‐tributoxyphenyl (TBP) groups having various electronic and steric demands as Ant units. Compound 5 a was prepared by the Suzuki‐Miyaura coupling of 1,8‐dichloroanthracene ( 4 ) and mesitylboronic acid [18] .…”

“…Compound 5 a was prepared by the Suzuki‐Miyaura coupling of 1,8‐dichloroanthracene ( 4 ) and mesitylboronic acid [18] . The Hartwig‐Miyaura borylation of 5 a afforded borylated compound 6 a almost quantitatively [7] . Compound 6 a was reacted with CuBr to give corresponding dibromo compound 7 a in 72 % yield [19] .…”

“…[18] The Hartwig-Miyaura borylation of 5 a afforded borylated compound 6 a almost quantitatively. [7] Compound 6 a was reacted with CuBr to give corresponding dibromo compound 7 a in 72 % yield. [19] The overall yield of 7 a prepared in three steps from 4 was 57 %, which was much higher than that in the preparation of the original building unit, 2,7-dibromo-10-mesitylanthracene, from 9-anthrone in five steps (3 %).…”

“…Among such noncovalent interactions, CH⋅⋅⋅π interactions [2,3] play an important role in the structures of organic crystals [4] and biomolecules [5] . However, supramolecular complexes associated mainly by CH⋅⋅⋅π interactions are rare because these interactions are weak and sensitive to the direction and distance of interacting moieties [2c,6,7] . Therefore, host‐guest systems driven by CH⋅⋅⋅π interactions need to be designed to maximize overall association energies in a precise manner.…”

Synthesis, Structures, and Complexation with Phenolic Guests of Acridone‐Incorporated Arylene–Ethynylene Macrocyclic Compounds

“…[5] Recently, they synthesized an all 2,7-anthrylene macrocycle, which included a [9]cycloparaphenylene molecule into the cavity. [6] These compounds inspired us to incorporate other aromatic units to create novel macrocycles having various properties. We then adopted 9(10H)-acridinone (acridone) units instead of anthracene units without changing the unit size, because the acridone structure has been applied in functional materials such as dyes, luminescent sensors, and electronic devices (Figure 1).…”