Rock‐Salt‐Type Crystal of Thermally Contracted C<sub>60</sub> with Encapsulated Lithium Cation

Aoyagi, Shinobu; Sado, Yuki; Nishibori, Eiji; Sawa, Hiroshi; Okada, Hiroshi; Tobita, Hiromi; Kasama, Yasuhiko; Kitaura, Ryo; Shinohara, Hisanori

doi:10.1002/anie.201108551

Cited by 80 publications

(81 citation statements)

References 33 publications

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“…Fullerene molecules often show rotational motion and orientation disorder in crystals. For instance, C 60 cages in [Li + @C 60 ](PF 6 − ) and pristine C 60 crystals show free rotational motion at high temperature [18,29]. The free rotational motions are stopped at low temperature by phase transitions at 370 K in [Li + @C 60 ](PF 6 − ) and 260 K in pristine C 60 .…”

Section: Resultsmentioning

confidence: 99%

“…Li + @C 60 forms crystalline salts with anions such as SbCl 6 − and PF 6 − [11,18]. The PF 6 − salt, [Li + @C 60 ](PF 6 − ), has a rock-salt-type cubic structure and shows a fast response to an alternating electric field by free rotational motion of the Li + cation on a shell with a radius of 1.5 Å inside the C 60 cage [18–20].…”

Section: Introductionmentioning

confidence: 99%

“…The PF 6 − salt, [Li + @C 60 ](PF 6 − ), has a rock-salt-type cubic structure and shows a fast response to an alternating electric field by free rotational motion of the Li + cation on a shell with a radius of 1.5 Å inside the C 60 cage [18–20]. The free rotational motion of the Li + cation is suppressed so that it is localized at two off-centre equivalent positions on the threefold inversion axis of the cubic crystal below 100 K. The simultaneous occupation of the two positions at low temperature is attributed to a quantum tunnelling of the Li + cation between the two positions with an interval of 2.7 Å.…”

Section: Introductionmentioning

confidence: 99%

“…Such anion exchange effects should be investigated in more depth to understand the electrostatic responses of the encapsulated Li + cations. Crystals of [Li + @C 60 ](PF 6 − ), [Li + @C 60 ](SbCl 6 − ) and [Li + @C 60 ](TFPB − ) (TFPB, tetrakis{3,5-bis(trifluoromethyl)phenyl}borate) were previously obtained and structurally characterized [11,18,21]. Further structural study of [Li + @C 60 ](TFPB − ) is required, because the position and motion of the Li + cation have not been revealed in the previous structural analysis [21].…”

Section: Introductionmentioning

confidence: 99%

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Structure of [60]fullerene with a mobile lithium cation inside

et al. 2018

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The structure of crystalline [60]fullerene with a lithium cation inside (Li+@C60) was determined by synchrotron radiation X-ray diffraction measurements to understand the electrostatic and thermal properties of the encapsulated Li+ cation. Although the C60 cages show severe orientation disorder in [Li+@C60](TFPB−)·C4H10O and [Li+@C60](TFSI−)·CH2Cl2, the Li+ cations are rather ordered at specific positions by electrostatic interactions with coordinated anions outside the C60 cage. The Li+@C60 molecules in [Li+@C60](ClO4−) with a rock-salt-type cubic structure are fully disordered with almost uniform spherical shell charge densities even at 100 K by octahedral coordination of ClO4− tetrahedra and show no orientation ordering, unlike [Li+@C60](PF6−) and pristine C60. Single-bonded (Li+@C60−)2 dimers in [Li+@C60−](NiOEP)⋅CH2Cl2 are thermally stable even at 400 K and form Li+–C bonds which are shorter than Li+–C bonds in [Li+@C60](PF6−) and suppress the rotational motion of the Li+ cations.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structure of [60]fullerene with a mobile lithium cation inside

et al. 2018

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“…25) [184], which can only be stabilized significantly in ambient conditions when it co-exists with an appropriate counteranion. For example, the crystal structure of the salt [Li À exhibits a strong interaction between Li + , residing inside the C 60 cage, and PF 6 À on the outside, the interaction being shown to occur through the six-membered rings [185].…”

Section: Endohedral Fullerenes: Improving Size Shape and Electronicmentioning

confidence: 99%

Buckyballs

Delgado

Filippone

Giacalone

et al. 2013

Topics in Current Chemistry

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Buckyballs represent a new and fascinating molecular allotropic form of carbon that has received a lot of attention by the chemical community during the last two decades. The unabating interest on this singular family of highly strained carbon spheres has allowed the establishing of the fundamental chemical reactivity of these carbon cages and, therefore, a huge variety of fullerene derivatives involving [60] and [70]fullerenes, higher fullerenes, and endohedral fullerenes have been prepared. Much less is known, however, of the chemistry of the uncommon non-IPR fullerenes which currently represent a scientific curiosity and which could pave the way to a range of new fullerenes. In this review on buckyballs we have mainly focused on the most recent and novel covalent chemistry of fullerenes involving metal catalysis and asymmetric synthesis, as well as on some of the most significant advances in supramolecular chemistry, namely H-bonded fullerene assemblies and the search for efficient concave receptors for the convex surface of fullerenes. Furthermore, we have also described the recent advances in the macromolecular chemistry of fullerenes, that is, those polymer molecules endowed with fullerenes which have been classified according to their chemical structures. This review is completed with the study of endohedral fullerenes, a new family of fullerenes in which the carbon cage of the fullerene contains a metal, molecule, or metal complex in the inner cavity. The presence of these species affords new fullerenes with completely different properties and chemical reactivity, thus opening a new avenue in which a more precise control of the photophysical and redox properties of fullerenes is possible. The use of fullerenes for organic electronics, namely in photovoltaic applications and molecular wires, complements the study and highlights the interest in these carbon allotropes for realistic practical applications. We have pointed out the so-called non-IPR fullerenes - those that do not follow the isolated pentagon rule - as the most intriguing class of fullerenes which, up to now, have only shown the tip of the huge iceberg behind the examples reported in the literature. The number of possible non-IPR carbon cages is almost infinite and the near future will show us whether they will become a reality.

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Molecular and Crystal Structures

Shinohara

Tagmatarchis

2015

Endohedral Metallofullerenes

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Rock‐Salt‐Type Crystal of Thermally Contracted C₆₀ with Encapsulated Lithium Cation

Abstract: Figure 1. Temperature dependence of the lattice constant of [Li + @C 60 ]-(PF 6 ) À measured for the single crystal (open circle) and powder sample (solid circle). The inset is the rock-salt-type fcc structure at a temperature above the T C value.

Cited by 80 publications

References 33 publications

Structure of [60]fullerene with a mobile lithium cation inside

Structure of [60]fullerene with a mobile lithium cation inside

Buckyballs

Molecular and Crystal Structures

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Rock‐Salt‐Type Crystal of Thermally Contracted C60 with Encapsulated Lithium Cation

Abstract: Figure 1. Temperature dependence of the lattice constant of [Li + @C 60 ]-(PF 6 ) À measured for the single crystal (open circle) and powder sample (solid circle). The inset is the rock-salt-type fcc structure at a temperature above the T C value.

Cited by 80 publications

References 33 publications

Structure of [60]fullerene with a mobile lithium cation inside

Structure of [60]fullerene with a mobile lithium cation inside

Buckyballs

Molecular and Crystal Structures

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Product

Resources

About

Rock‐Salt‐Type Crystal of Thermally Contracted C₆₀ with Encapsulated Lithium Cation