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/anie.201105360

Cited by 28 publications

(8 citation statements)

References 29 publications

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“…At ambient temperature the corresponding fine structure in the EPR spectrum is not resolved owing to fast rotation of the C 60 molecules. An analogous behavior has most recently been reported for C 60 – fulleride anions, which has been ascribed to a transition from static to dynamic Jahn–Teller effect 21. The small admixture of a C 60 3– anion with S = 1/2 can tentatively be ascribed to a hopping mechanism of electrons from the fulleride anion to the cation matrix or an impurity of a C 60 3– salt 8.…”

Section: Resultssupporting

confidence: 72%

Three Salts Containing the Fullerene Tetra‐Anion C₆₀^4– – Synthesis, X‐Ray Single‐Crystal Structure Determination and EPR Investigation

Boeddinghaus

Wahl

Fässler

et al. 2012

Zeitschrift anorg allge chemie

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A synthesis for four-fold negatively charged fullerides in solution is presented. Three salts containing discrete C 60 4anions were synthesized by the reduction of C 60 in solution using rubidium-mercury amalgams and rubidium suboxide both in the presence of elemental mercury. The three new salts, [Rb 6 DMF 14 (C 6 H 13 N 2 O 2 ) 2 ]· C 60 (1), [Rb(diaza-18-crown-6)] 4 ·C 60 ·(en) 4.1 (2), and [Rb(benzo-18crown-6)] 4 ·C 60 (3), were characterized by single-crystal X-ray diffrac-

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Section: Resultssupporting

confidence: 72%

Three Salts Containing the Fullerene Tetra‐Anion C₆₀^4– – Synthesis, X‐Ray Single‐Crystal Structure Determination and EPR Investigation

Boeddinghaus

Wahl

Fässler

et al. 2012

Zeitschrift anorg allge chemie

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“…Jahn-Teller distortion in fullerides is relatively small, but can in some cases be observable by structural studies. 13,32 We did, however, observe that the two carbon centres that terminally coordinate the Mg centres are signicantly more pyramidalized, slightly protrude from the fulleride "sphere" and show C/C 60-centroid distances that are 0.09-0.10Å longer than the mean from the remaining 58 distances. Also, the fulleride C-C bond lengths in 3b 0 cannot be analysed due to poor ordering and low bond precision.…”

Section: Resultsmentioning

confidence: 62%

Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium

et al. 2019

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“…Vibrational analyses were performed to verify that the optimized structures are local minima. For anionic species, the polarizable continuum model was incorporated by considering a conductor‐like screening model treatment via the COSMO module with tetrahydrofuran (THF) as solvent, to take into account the effects of polar solvents usually employed in such compounds …”

Section: Computational Detailsmentioning

confidence: 99%

Fulfilling the 2(N+1)² Hirsch rule in smaller hollow fullerenes. Evaluation of long‐range magnetic behavior and NMR patterns of C₂₈, _, C₂₄N_4, and C₂₈H₄

Muñoz-Castro

2018

Int J of Quantum Chemistry

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The formation of different 32 p-electron systems derived from a prominent small fullerene given by C 28 , allows to evaluate several approaches ensuring an electronic shell closure in terms of the characteristic chemical shift anisotropy (CSA) and long-range magnetic response properties for spherical aromatic compounds. Our results show that the inclusion of extra electrons and the doping of the cage, are able to sustain a long-range shielding cone when an external field is oriented in a specific orientation. Such properties are inherent characteristics of spherical aromatic compounds, which are not obtained in the neutral C 28 fullerene, and in the exo-bonded approach leading to C 28 H 4 . Thus, the doping of the cage is suggested as the most suitable approach to modify the overall count of electrons, leading to the expected response properties for further design of highly aromatic fullerenes.fullerenes, heterofullerenes, magnetic response, spherical aromaticity 1 | I N TR ODU C TI ON Carbon-based nanomaterials have attracted considerable attention since the discovery of fullerenes where many efforts have been devoted to understand their important physical and chemical properties. [1][2][3][4] Most studies of fullerenes are related to C 60 or larger cages, [3,[5][6][7][8][9][10] however, smaller structures containing fewer carbon atoms have also been reported. [3,[11][12][13] Such cages are particularly interesting owing to their high-curved surfaces provided by adjacent five-membered faces. C 20 is the smallest possible example of a fullerene cage composed solely by pentagonal faces leading to a highly strained structure detected as short-lived species. [14] As a result, fullerenes within 24 to 32 atoms are expected to be prone to reduce the strain toward more favorable cages, with C 28 showing a particularly stability given by its larger abundance related to other counterparts. [13,[15][16][17] Since the early work of Kroto on the stability of smaller fullerenes, [15] C 28 has been considered as a tetrahedral cage with an open-shell electronic structure. [16,18] A plausible strategy to achieve an electronic shell closing retaining the hollow fullerene cage, is to achieve the closest magic number of valence electrons (ve) which amounts to 32-ve, as has been explored previously since the early description of C 28 fullerene. [19] According to the enhanced stability expected by the electronic shell closure situation, several-related structures has been proposed theoretically through the years. [11,17,[20][21][22][23] In this sense, C 28 42 , C 24 N 4 , and C 28 H 4 have been described to introduce extra electrons to the p-electron system.Such systems fulfill the Hirsch 2(N 1 1) 2 rule [24][25][26][27] (N 5 3) for spherical aromaticity, where an external field induces a current circulation of electrons giving rise to an induced magnetic field opposing (shielding) the external field at the center of the ring. This induced magnetic field is complemented by a deshielding region at the outer contour as recently discuss...

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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 28 publications

References 29 publications

Three Salts Containing the Fullerene Tetra‐Anion C₆₀^4– – Synthesis, X‐Ray Single‐Crystal Structure Determination and EPR Investigation

Three Salts Containing the Fullerene Tetra‐Anion C₆₀^4– – Synthesis, X‐Ray Single‐Crystal Structure Determination and EPR Investigation

Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium

Fulfilling the 2(N+1)² Hirsch rule in smaller hollow fullerenes. Evaluation of long‐range magnetic behavior and NMR patterns of C₂₈, _, C₂₄N_4, and C₂₈H₄

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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 28 publications

References 29 publications

Three Salts Containing the Fullerene Tetra‐Anion C604– – Synthesis, X‐Ray Single‐Crystal Structure Determination and EPR Investigation

Three Salts Containing the Fullerene Tetra‐Anion C604– – Synthesis, X‐Ray Single‐Crystal Structure Determination and EPR Investigation

Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium

Fulfilling the 2(N+1)2 Hirsch rule in smaller hollow fullerenes. Evaluation of long‐range magnetic behavior and NMR patterns of C28, , C24N4, and C28H4

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

Three Salts Containing the Fullerene Tetra‐Anion C₆₀^4– – Synthesis, X‐Ray Single‐Crystal Structure Determination and EPR Investigation

Three Salts Containing the Fullerene Tetra‐Anion C₆₀^4– – Synthesis, X‐Ray Single‐Crystal Structure Determination and EPR Investigation

Fulfilling the 2(N+1)² Hirsch rule in smaller hollow fullerenes. Evaluation of long‐range magnetic behavior and NMR patterns of C₂₈, _, C₂₄N_4, and C₂₈H₄