Through-space π-delocalization in a conjugated macrocycle consisting of [2.2]paracyclophane

Wu, Yayu; Zhuang, Guilin; Cui, Shengsheng; Zhou, Yu; Wang, Jinyi; Huang, Qiang; Du, Pingwu

doi:10.1039/c9cc06492c

Cited by 21 publications

(15 citation statements)

References 48 publications

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“…The significantly enhanced stability of 2 is in line with its lack of thermally accessible triplet species and low intrinsic strain (vide supra). The absorption spectra measured in CH 2 Cl 2 for 1a, 1b, and 2 exhibited one intense peak at around 320 nm and one or two weak shoulder peaks in the region of 350−540 nm, indicating a combined feature of carbon nanohoop 56 and folded OCE chromophores. Lower energy transitions arising from twisted structures were not observed.…”

Section: ■ Results and Discussionmentioning

confidence: 94%

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

et al. 2021

J. Am. Chem. Soc.

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The design and preparation of molecular systems with multiple geometric and electronic configurations are the cornerstones for multifunctional materials with stimuli-responsive behaviors. We describe here the regioselective and facile synthesis of two types of overcrowded ethylene-bridged nanohoop dimers, with folded and twisted geometric structures as well as closed-shell, diradical and dication electronic structures. The strained nanohoop structures have a profound effect on the overall molecular and electronic configurations, which resulted in the destabilized diradical state. X-ray crystallographic analysis revealed the folded molecular geometry for the neutral species and twisted geometry for the dication species. The unique molecular dynamics, optical properties, and dynamic redox properties were disclosed in the solution phase by spectroscopic and electrochemical methods. Furthermore, the global Hückel and Möbius aromaticity were revealed by a combination of experimental and theoretical approaches. Our studies shed light on the design of nanohoop-incorporated multiconfigurational materials with unique topologies and functions.

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Section: ■ Results and Discussionmentioning

confidence: 94%

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

et al. 2021

J. Am. Chem. Soc.

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“…However, the functionalization of planar chiral [2.2]PCP as a chiral building block for the construction of macrocycles still remains underexplored [14] . Recently, [2.2]PCP containing benzene‐based macrocycle was reported, but no chiral property was disclosed [14e] . Inspiring by the planar chirality of [2.2]PCP, we envisioned that the integration of a planar chiral [2.2]PCP unit with achiral CPPs should generate novel chiral carbon macrocycles with appealing chiral properties by efficient transfer of the planar chirality of [2,2]PCP (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Nanosized Carbon Macrocycles Based on a Planar Chiral Pseudo Meta‐[2.2]Paracyclophane

Pang

et al. 2022

Chemistry A European J

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Structural designs combining cycloparaphenylenes (CPPs) backbone with planar chiral [2.2]paracyclophane ([2.2]PCP) lead to optical‐active chiral macrocycles with intriguing properties. X‐ray crystal analysis revealed aesthetic necklace‐shaped structures and size‐dependent packages with long‐range channels. The macrocycles exhibit unique photophysical properties with high fluorescence quantum yield of up to 82 %, and the fluorescent color varies with ring size. In addition, size‐dependent chiroptical properties with moderately large CPL dissymmetry factor of 10−3 and CPL brightness in the range of 30–40 M−1 cm−1 were observed.

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“…They have been used among other things for the construction of dendrimer structures, 22 macrocyclic metal complexes, 23 or one-handed double helices. 24 Recently, pseudo-para PCP was also incorporated into CPPs to investigate through-space conjugation 25 and a fourfold substituted PCP was used for helical chirality stabilization in oligothiophene macrocycles. 26 Triangle-shaped macrocycles consisting of peudo-ortho PCPs with either para-phenylene-ethynylene or biphenyl linkers 27 were also reported, but their angle only allows the formation of limited ring sizes.…”

Section: Introductionmentioning

confidence: 99%

Intense Molar Circular Dichroism in Fully Conjugated All-Carbon Macrocyclic 1,3-Butadiyne Linked pseudo-meta [2.2]Paracyclophanes

Sidler

Zwick

Mayor

2022

Preprint

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The synthetic access to macrocyclic molecular topologies with interesting photophysical properties has greatly improved thanks to the successful implementation of organic and inorganic corner units. Based on recent reports, we realized pseudo-meta [2.2]paracyclophanes (PCPs) might serve as optimal corner units for constructing 3D functional materials, owing to their efficient electronic communication, angled substituents and planar chirality. Herein, we report the synthesis, characterization and optical properties of three novel all-carbon enantiopure macrocycles bearing three to five pseudo-meta PCPs linked by 1,3-butadiyne units. The macrocycles were obtained by a single step from enantiopure literature known dialkyne pseudo-meta PCP and were unambiguously identified and characterized by state-of-the-art spectroscopic methods. By comparing the optical properties to relevant reference compounds, we show that the pseudo-meta PCP subunit effectively elongates the conjugated system throughout the macrocyclic backbone, such that already the smallest macrocycle consisting of only three subunits reaches an astounding polymer-like conjugation length. Additionally, we show that the chiral pseudo-meta PCPs induce remarkable chiroptical response in the respective macrocycles, which increases non-linearly with the number of PCP units to unprecedented high molar dichroism values for all-carbon macrocycles of up to 1335 L mol-1 cm-1.

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Through-space π-delocalization in a conjugated macrocycle consisting of [2.2]paracyclophane

Abstract: Herein, we report the synthesis and characterization of a [2.2]paracyclophane-containing macrocycle (PCMC) as a new through-space conjugated macrocycle using only benzene groups as the skeleton.

Cited by 21 publications

References 48 publications

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

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

Nanosized Carbon Macrocycles Based on a Planar Chiral Pseudo Meta‐[2.2]Paracyclophane

Intense Molar Circular Dichroism in Fully Conjugated All-Carbon Macrocyclic 1,3-Butadiyne Linked pseudo-meta [2.2]Paracyclophanes

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