Direct Observation of the Transition from Static to Dynamic Jahn–Teller Effects in the [Cs(THF)<sub>4</sub>]C<sub>60</sub> Fulleride

Amsharov, Konstantin; Krämer, Yvonne; Jansen, Martin

doi:10.1002/ange.201105360

Cited by 14 publications

(25 citation statements)

References 29 publications

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“…C 60 -fullerene can potentially accept up to six extra electrons owing to its triply degenerate and low-lying LUMOs. [3] While all six reduction steps were observed in solution by cyclic voltammetry, [4] so far only mono-through tetraanions [5] of C 60 have been crystallographically characterized. The smallest non-planar fragment of the C 60 -fullerene, corannulene (C 20 H 10 ; Scheme 1), has a doubly degenerate LUMO and can thus accept up to four electrons.…”

Section: Dedicated To Professor Roald Hoffmann On the Occasion Of Hismentioning

confidence: 97%

“…The initial reduction of C 20 H 10 with mixtures of Li and Na in [D 8 ]THF revealed the formation of the known Li 5 aggregate, identified by a characteristic 7 Li NMR singlet at À11.7 ppm. [9,11,18] On the contrary, while the formation of four-fold reduced corannulene was clearly observed in the reaction mixture with Li and K metals, the assignment of the specific products in solution was problematic.…”

Section: Dedicated To Professor Roald Hoffmann On the Occasion Of Hismentioning

confidence: 98%

“…After numerous attempts and variations of experimental conditions, we have successfully crystallized the product from a diglyme/THF solution. The single-crystal Xray diffraction analysis revealed the formation of an unprecedented mixed-alkali-metal LiK 5 Figure 1). All of the Li + ions that were encapsulated between the sixmembered rings of C 20 H 10 4À in the Li 5 structure have been replaced by K + ions.…”

Section: Dedicated To Professor Roald Hoffmann On the Occasion Of Hismentioning

confidence: 99%

“…2.0 . The K···C contacts to the sixmembered rings of C 20 H 10 4À range from 2.905(5) to 3.491 (5) .…”

Section: Dedicated To Professor Roald Hoffmann On the Occasion Of Hismentioning

confidence: 99%

“…Abstract: The first members of a new class of supramolecular organometallic compounds with mixed-alkali-metal cluster cores, LiK 5 , illustrate a record ability of bowl-shaped and highly charged corannulene to provide all its sites, five benzene rings fused to a central five-membered ring, for binding of six alkali-metal ions. The previously unseen engagement of the hub-site of C 20 H 10 4À in lithium binding is accompanied by unprecedented shifts up to À24 ppm in 7 Li NMR spectra.…”

Section: Dedicated To Professor Roald Hoffmann On the Occasion Of Hismentioning

confidence: 99%

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

et al. 2013

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Section: Dedicated To Professor Roald Hoffmann On the Occasion Of Hismentioning

confidence: 97%

Section: Dedicated To Professor Roald Hoffmann On the Occasion Of Hismentioning

confidence: 98%

Section: Dedicated To Professor Roald Hoffmann On the Occasion Of Hismentioning

confidence: 99%

“…2.0 . The K···C contacts to the sixmembered rings of C 20 H 10 4À range from 2.905(5) to 3.491 (5) .…”

Section: Dedicated To Professor Roald Hoffmann On the Occasion Of Hismentioning

confidence: 99%

Section: Dedicated To Professor Roald Hoffmann On the Occasion Of Hismentioning

confidence: 99%

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

et al. 2013

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Pentadecker Supramolecules with a Lithium Alkoxo Nanobelt Sandwiched between Two Highly Charged Buckybowl Surfaces

et al. 2012

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Stapeln angesagt: Bei der Reduktion von Corannulen mit Lithiummetall im Überschuss in Dimethoxyethan (DME) entstehen verblüffende mehrschichtige supramolekulare Aggregate (siehe Bild), in denen Lithiumalkoxo‐Nanogürtel zwischen zwei vierfach reduzierten Corannulen‐Schalen eingeschlossen sind, [C20H104−/Li6(OR)6Li6/C20H104−]2−. Die Alkoxogruppen (R=CH3O oder/und CH3OCH2CH2O) sind Produkte der Li‐induzierten Spaltung von DME.

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Counterintuitive Anisotropy of Electron Transport Properties in KC₆₀(THF)₅⋅2 THF Fulleride

et al. 2013

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The discovery of unique physical properties possessed by alkali metal fullerides A x C 60 (x = 1-3, A = K, Rb, Na, Cs) such as conductivity and superconductivity has prompted intensive investigation in recent years with regards to these materials. [1] Nevertheless, the exact nature of the electronic properties exhibited by fulleride-based solids is not yet fully clarified and still remains a much discussed subject in many research groups worldwide. As a basis for the deeper understanding of fulleride properties and the further elaboration of a structureproperty relationship, detailed knowledge of their structural features is indispensable. Single-crystal X-ray structure determination is the most powerful experimental technique for detailed structural analysis; unfortunately, progress in this field with respect to fulleride characterization has been slow because of difficulties in the synthesis of high-quality single crystals containing fullerene anions. As a rule, the fulleride crystals are twinned and frequently suffer orientation disorder of the sphere-like C 60 anions. [2] Moreover, the strong tendency of C 60 anion radicals to recombine and form diamagnetic single-bonded (C 60 ) 2 2À ions, [3] has further impaired the ability to obtain the requisite close-packed C 60 C À structures essential for manifestation of conductivity. As a matter of fact, only a few high-quality structures have been reported to date, where individual C 60 anion radicals have remained separated at low temperatures. [4] Recently, a 2Dlayered structure in which C 60 anion radicals form a 2D honeycomb sublattice with short fullerene-to-fullerene distances has been reported and investigated. [5] The compound was found to be a fascinating example of the first fullerenebased two-dimensional organic metal to be described. In contrast, a later reported 2D-layered structure of CsC 60 -(THF) 4 comprising layers of an atypical square-shaped configuration of fully ordered fullerene anion radicals with short C 60 -C 60 center-to-center distances has shown no sign of conductivity. [6] These findings clearly point to the importance of the relative orientational configuration of fullerene anions in the crystal for manifestation of conductivity phenomena in the solid state.Herein, we report the combined results of investigations into the electronic and structural properties of KC 60 -(THF) 5 ·2 THF single crystals. The title compound exhibits a unique 2D arrangement of C 60 anion radicals, in which corrugated layers are formed with close fullerene-fullerene contacts. Important findings include the presence of onedimensional electric conductivity and the observation of a counterintuitive anisotropy for electron transport. A detailed crystallographic and spectroscopic study carried out with individual single crystals, together with quantum chemical calculations, reveals the main factors responsible for effective interactions between fullerene anions leading to the manifestation of conductivity in fullerides.The C 60 anion radicals were obtained from sol...

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Direct Observation of the Transition from Static to Dynamic Jahn–Teller Effects in the [Cs(THF)₄]C₆₀ Fulleride

Cited by 14 publications

References 29 publications

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

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

Pentadecker Supramolecules with a Lithium Alkoxo Nanobelt Sandwiched between Two Highly Charged Buckybowl Surfaces

Counterintuitive Anisotropy of Electron Transport Properties in KC₆₀(THF)₅⋅2 THF Fulleride

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Direct Observation of the Transition from Static to Dynamic Jahn–Teller Effects in the [Cs(THF)4]C60 Fulleride

Cited by 14 publications

References 29 publications

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

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

Pentadecker Supramolecules with a Lithium Alkoxo Nanobelt Sandwiched between Two Highly Charged Buckybowl Surfaces

Counterintuitive Anisotropy of Electron Transport Properties in KC60(THF)5⋅2 THF Fulleride

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Product

Resources

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Direct Observation of the Transition from Static to Dynamic Jahn–Teller Effects in the [Cs(THF)₄]C₆₀ Fulleride

Counterintuitive Anisotropy of Electron Transport Properties in KC₆₀(THF)₅⋅2 THF Fulleride