Clamshell Opening in the Mixed‐Metal Supramolecular Aggregates Formed by Fourfold Reduced Corannulene for Maximizing Intercalated Metal Content

Filatov, Alexander S.; Zabula, Alexander V.; Spisak, Sarah N.; Rogachev, Andrey Yu.; Petrukhina, Marina A.

doi:10.1002/ange.201308090

Cited by 26 publications

(1 citation statement)

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“…The smallest curved subunits of C 60 , corannulene, [8–12] and sumanene, [13, 14] have been exhaustively investigated and serve as scaffolds for the syntheses of diverse, topologically unique molecular nanocarbons [15–19] . On top of the pursuit of well‐defined carbon‐rich materials, [20–23] multifaceted research on bowl‐shaped nanographenes contributes to fundamental science, addressing questions regarding the nature of aromaticity, [24–26] strain energies, [27, 28] and metal complexation [29] . Inducing a curvature in π‐extended systems, usually requires harsh conditions which rarely tolerate electron‐rich heterocycles.…”

Section: Introductionmentioning

confidence: 99%

Bowl‐Shaped Pentagon‐ and Heptagon‐Embedded Nanographene Containing a Central Pyrrolo[3,2‐b]pyrrole Core

et al. 2021

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A bowl‐shaped nitrogen‐doped nanographene composed of a pyrrolo[3,2‐b]pyrrole core substituted with six arene rings circularly bonded with one another has been prepared via a concise synthetic strategy encompassing the multicomponent tetraarylpyrrolopyrrole (TAPP) synthesis, the Scholl reaction, and intramolecular direct arylation. This synthesis represents the first case of programmed sequential intramolecular direct arylation reactions utilizing the different reactivity of C–Br and C–Cl bonds. The target compound contains two central pentagons confined between two adjacent heptagons—the inverse Stone–Thrower–Wales topology. The presence of both five‐ and seven‐membered rings in the final structure is responsible for interesting properties such as a perpendicularly aligned dipole moment, absorption and fluorescence in the orange‐red region, weak emission originating from the charge‐transfer character of a low‐energy absorption band, and a high lying HOMO. In the solid state slipped convex‐to‐convex π–π stacking dominates.

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Section: Introductionmentioning

confidence: 99%

Bowl‐Shaped Pentagon‐ and Heptagon‐Embedded Nanographene Containing a Central Pyrrolo[3,2‐b]pyrrole Core

et al. 2021

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Ring Reconstruction on a Trichalcogenasumanene Buckybowl: A Facile Approach to Donor–Acceptor‐Type [5‐6‐7] Fused Planar Polyheterocycles

Zhu

Shao

et al. 2014

Angewandte Chemie

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The transformation of trichalcogenasumanene buckybowls into donor-acceptor-type [5-6-7] fused polyheterocycles is disclosed. The strategy involves a highly efficient ring-opening of the flanking benzene upon oxidation at room temperature, and facile ring closure by functionalgroup transformation. Crystallographic studies indicate that the resulting [5-6-7] fused polyheterocycles possess a planar conformation owing to the release of ring strain by expansion of one of the six-membered flanking rings to the sevenmembered one. Additionally, the [5-6-7] fused polyheterocycles bear electron-withdrawing groups, which reduce the HOMO-LUMO energy gap, and display broad absorption bands extending to l = 590 nm. Consequently, these compounds show strong red emission with fluorescence quantum yields of up to 38 %.

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Redox‐Active Corannulene Buckybowls in a Crystalline Hybrid Scaffold

et al. 2015

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Ap orous crystalline corannulene-containing scaffold, whichc ombines the periodicity,d imensionality,a nd structural modularity of hybrid frameworks with the intrinsic properties of redox-active p-bowls,has been prepared. Singlecrystal and powder X-ray diffraction, ab initio density functional theory computations,gas sorption analysis,fluorescence spectroscopy, and cyclic voltammetry were employed to study the properties of the novel corannulene derivatives and the buckybowl-based hybrid materials.X -rayd iffraction studies revealed the preservation of the corannulene bowl inside the prepared rigid matrix, which offers the unique opportunity to extend the scaffold dimensionality through the buckybowl curvature.M erging the inherent properties of hybrid frameworks with the intrinsic properties of p-bowls opens an ew avenue for preparing redox-active materials and potentially improving charge transport in the scaffold.The bowl-shaped surface of corannulene,C 20 H 10 ,h as attracted al ot of attention owing to its intriguing curvature.[1-6] However,o nly recently am ore practical synthetic route [7] rendered C 20 H 10 available for comprehensive studies, which has also boosted its utilization in aw ide scope of applications. [8][9][10][11][12][13][14] Fori nstance,a cceptance of four electrons makes corannulene more electron-rich per carbon atom than the commonly used electron acceptor fullerene. [15,16] Moreover, the electron-accepting properties can be tuned through derivatization of the C 20 H 10 bowl.[17] Corannulene also possesses ah igh degree of lithium intercalation, as exemplified by the sandwich-like structure consisting of two corannulene tetraanions with five lithium cations incorporated between them (Scheme 1).[15] Furthermore,t he reversible lithium capacity of corannulene-based materials is almost twice as high as that of lithiated graphite, [18] rendering corannulene derivatives promising building blocks for the preparation of anode materials in rechargeable lithium-ion batteries.Herein, we report the development of ahybrid framework built from novel redox-active corannulene-based ligands.I n contrast to previously reported corannulene-containing polymers, [19][20][21][22][23] we have synthesized the first example of ap orous crystalline scaffold in which the derivatized buckybowl is covalently linked to metal ions.Coordinative immobilization of the corannulene-based linker inside the metal-organic framework (MOF) preserves the bowl shape,which may offer an extension of scaffold dimensionality through the corannulene curvature.B ya nalogy with the reduced corannulenebased "sandwich", [15,24] the prepared crystalline scaffold can be considered a" baguette", for instance,f or alkali-metal intercalation (Scheme 1). Moreover,i ncorporation of redoxactive corannulene-based ligands opens an ew avenue to improve MOF charge-transport properties and develop anew family of electrochromic materials.I nt he presented work, single-crystal and powder X-ray crystallography,spectroscopic studies,gas sorpti...

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Clamshell Opening in the Mixed‐Metal Supramolecular Aggregates Formed by Fourfold Reduced Corannulene for Maximizing Intercalated Metal Content

Abstract: The first members of a new class of supramolecular organometallic compounds with mixed-alkali-metal cluster cores, LiK 5 and Li 3 K 3 , sandwiched between two four-fold reduced corannulene decks are prepared and fully characterized.

Cited by 26 publications

References 50 publications

Bowl‐Shaped Pentagon‐ and Heptagon‐Embedded Nanographene Containing a Central Pyrrolo[3,2‐b]pyrrole Core

Bowl‐Shaped Pentagon‐ and Heptagon‐Embedded Nanographene Containing a Central Pyrrolo[3,2‐b]pyrrole Core

Ring Reconstruction on a Trichalcogenasumanene Buckybowl: A Facile Approach to Donor–Acceptor‐Type [5‐6‐7] Fused Planar Polyheterocycles

Redox‐Active Corannulene Buckybowls in a Crystalline Hybrid Scaffold

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