Toward Möbius and Tubular Cyclopolyarene Nanorings via Arylbutadiyne Macrocycles

Abstract

By harnessing a highly efficient metal‐catalyzed tandem cycloaddition reaction as the key benzannulation step, a series of cyclopolyarene nanorings of varied sizes are obtained from poly(arylene‐butadiynylene) macrocyclic precursors, which can be synthesized relatively conveniently. Interestingly, due to the nonparallel bond connectivity of the repeat unit, unique Möbius topology is manifested by the cyclopolyarene nanorings composed of an odd number of repeat units, whereas cylindrical tubular structures with radial conjugation are formed with those consisting of an even number of repeat units.

Overcrowded Ethylene-Bridged Nanohoop Dimers: Regioselective Synthesis, Multiconfigurational Electronic States, and Global Hückel/Möbius Aromaticity

“…Interestingly, global Hückel and Möbius aromaticity for the dication and diradical species were revealed by X-ray crystallographic analysis, proton NMR, and calculations. Studies on the ring-size effect of the nanohoop, the dehydrogenation reaction to afford condensed polycyclic systems, and preparation of molecular systems with Möbius geometry , and aromaticity are of great interest in the future.…”

Coexistence of Parallel and Rotary Stackings in the Lamellar Crystals of a Perylene Bisimide Dyad for Temperature-Sensitive Bicomponent Emission

“…In the past decades, perylene bisimides (PBIs) were intensively investigated as building blocks for the construction of functional supramolecular assemblies based on the directional intermolecular π–π interactions and hydrogen bonding. , Numerous self-assembled aggregates and nanocrystals were fabricated with either H- or J-type coupling. − However, irrespective of the coupling, they still suffered from ACQ in condensed states. , One example is that singlet fission in the nanocrystals of bay-area nitro-substituted PBI with parallel intermolecular stacking resulted in efficient formation of nonradiative triplet excited states through an intermolecular symmetry-breaking charge separation (SB-CS) process …”

Syntheses of Anthracene‐Centered Large PAH Diimides and Conjugated Polymers**

“…[13] Recently, we used this reaction to make cyclopolyarene nanorings of varied size exhibiting unique Möbius and tubular topology. [14] Liu [15] and Miao [16] further applied this protocol to suitably multi-functionalized substrates and successfully accomplished double and triple benzannulation processes.…”

“…Copper‐catalyzed [4+2] cycloaddition between alkynes and o ‐phenylethynylbenzaldehyde, first developed by Yamamoto and Asao, [12] has been serving as a potent method for preparing different naphthalene derivatives [13] . Recently, we used this reaction to make cyclopolyarene nanorings of varied size exhibiting unique Möbius and tubular topology [14] . Liu [15] and Miao [16] further applied this protocol to suitably multi‐functionalized substrates and successfully accomplished double and triple benzannulation processes.…”