Aromatic hydrocarbon belts

Guo, Qing‐Hui; Qiu, Yan; Wang, Mei‐Xiang; Stoddart, J. Fraser

doi:10.1038/s41557-021-00671-9

Cited by 144 publications

(115 citation statements)

References 219 publications

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“…The building blocks with oxygen bridges fulfilled the necessity for preorganization, thus favoring cage formation. However, the deoxygenation/dehydration/dehydrogenation reactions that aimed to aromatize the structure to give a fully fused, three-dimensional (3D) π-conjugated cage are challenging due to large strain and high reactivity, as demonstrated by the attempted synthesis of a [12]cyclacene carbon nanobelt by the same strategy. − Thus, it is crucial to develop new synthetic strategies to circumvent both preorganization and large strain for the preparation of such cage.…”

Section: Introductionmentioning

confidence: 99%

Facile Synthesis of a Fully Fused, Three-Dimensional π-Conjugated Archimedean Cage with Magnetically Shielded Cavity

Zhu

Han

et al. 2021

J. Am. Chem. Soc.

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The synthesis of molecular cages consisting of fully fused, π-conjugated rings is rare due to synthetic challenges including preorganization, large strain, and poor solubility. Herein, we report such an example in which a tris-2-aminobenzophenone precursor undergoes acid-mediated self-condensation to form a truncated tetrahedron, one of the 13 Archimedean solids. Formation of eight-membered [1,5]diazocine rings provides preorganization and releases the strain while still maintains weak π-conjugation of the backbone. Thorough characterizations were performed by X-ray, NMR, and UV−vis analysis, assisted by theoretical calculations. The cage exhibits a rigid backbone structure with a well-defined cavity that confines a magnetically shielded environment. The solvent molecule, o-dichlorobenzene, is precisely encapsulated in the cavity at a 1:1 ratio with multiple π•••π, C−H•••π, and halogen•••π interactions with the cage skeleton, implying its template effect for the cage closing reaction. Our synthetic strategy opens the opportunity to access more complex, fully fused, three-dimensional π-conjugated cages.

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Section: Introductionmentioning

confidence: 99%

Facile Synthesis of a Fully Fused, Three-Dimensional π-Conjugated Archimedean Cage with Magnetically Shielded Cavity

Zhu

Han

et al. 2021

J. Am. Chem. Soc.

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“…Oxanorbornene-fused double-stranded macrocycles, represented by kohnkene (Fig. 1a), have received considerable attention not only because they are synthetic precursors toward short segments of zigzag carbon nanotubes 1–6 but also because they are typical cavitands processing well defined cavities as a result of the intrinsic curvature of the oxanorbornene moieties. 7 Kohnkene was synthesized by Kohnke, Stoddart and co-workers in 1987 during the targeted synthesis of [12]cyclacene, 8,9 and named after its creator.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, aromatization and cavitates of an oxanorbornene-fused dibenzo[de,qr]tetracene nanobox

2022

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“…1) with a weak intermolecular interaction, so that the diradical character can be preserved in the crystal phase. These aromatic hydrocarbon nanobelts [15] are very appealing molecules and are the subject of strong interest, both theoretically and experimentally. In the gas phase, the local moments are hosted by molecular orbitals that are topological symmetry protected zero modes [16].…”

Section: Introductionmentioning

confidence: 99%

Frustrated magnetic interactions in a cyclacene crystal

Ortiz

Sancho‐García

Fernández-Rossier

2022

Phys. Rev. Materials

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We study the emergence of magnetism and its interplay with structural properties in a two-dimensional molecular crystal of cyclacenes, using density functional theory (DFT). Isolated cyclacenes with an even number of fused benzenes host two unpaired electrons in two topological protected zero modes, at the top and bottom carbon rings that form the molecule. We show that, in the gas phase, electron repulsion promotes an open-shell singlet with strong intramolecular antiferromagnetic exchange. We consider a closed packing triangular lattice crystal phase and we find a strong dependence of the band structure and magnetic interactions on the rotation angle of the cyclacenes with respect to the crystal lattice vectors. The orientational ground state maximizes the intermolecular hybridization, yet local moments survive. Intermolecular exchange is computed to be antiferromagnetic, and DFT predicts a broken symmetry 120 • spin phase reflecting the frustration of the intermolecular spin coupling. Thus, the cyclacene crystal realizes a bilayer of two antiferromagnetically coupled S = 1/2 triangular lattices. Our results provide a bottom-up route towards carbon based strongly correlated platforms in two dimensions.

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Aromatic hydrocarbon belts

Cited by 144 publications

References 219 publications

Facile Synthesis of a Fully Fused, Three-Dimensional π-Conjugated Archimedean Cage with Magnetically Shielded Cavity

Facile Synthesis of a Fully Fused, Three-Dimensional π-Conjugated Archimedean Cage with Magnetically Shielded Cavity

Synthesis, aromatization and cavitates of an oxanorbornene-fused dibenzo[de,qr]tetracene nanobox

Frustrated magnetic interactions in a cyclacene crystal

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