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

Aoyagi, Shinobu; Miwa, Kazuhira; Ueno, Hiroshi; Okada, Hiroshi; Kokubo, Ken

doi:10.1098/rsos.180337

Cited by 17 publications

(15 citation statements)

References 37 publications

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“…1b ), and the shell-like Li + ion is off-centred and localised above or below the Cu plane with thermal ellipsoids at 50% probability. Similar Li + -ion arrangements are also observed in the other forms of Li + @C 60 salts 37 , 38 . The inner Li + ion coordinates with the six-carbon ring with Li–C bond lengths in the range of 2.337–2.527 Å, which are consistent with the reported results 7 , 39 .…”

Section: Resultssupporting

confidence: 74%

Heterospin frustration in a metal-fullerene-bonded semiconductive antiferromagnet

et al. 2022

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Lithium-ion-encapsulated fullerenes (Li+@C60) are 3D superatoms with rich oxidative states. Here we show a conductive and magnetically frustrated metal–fullerene-bonded framework {[Cu4(Li@C60)(L)(py)4](NTf2)(hexane)}n (1) (L = 1,2,4,5-tetrakis(methanesulfonamido)benzene, py = pyridine, NTf2− = bis(trifluoromethane)sulfonamide anion) prepared from redox-active dinuclear metal complex Cu2(L)(py)4 and lithium-ion-encapsulated fullerene salt (Li+@C60)(NTf2−). Electron donor Cu2(L)(py)2 bonds to acceptor Li+@C60 via eight Cu‒C bonds. Cu–C bond formation stems from spontaneous charge transfer (CT) between Cu2(L)(py)4 and (Li+@C60)(NTf2−) by removing the two-terminal py molecules, yielding triplet ground state [Cu2(L)(py)2]+(Li+@C60•−), evidenced by absorption and electron paramagnetic resonance (EPR) spectra, magnetic properties and quantum chemical calculations. Moreover, Li+@C60•− radicals (S = ½) and Cu2+ ions (S = ½) interact antiferromagnetically in triangular spin lattices in the absence of long-range magnetic ordering to 1.8 K. The low-temperature heat capacity indicated that compound 1 is a potential candidate for an S = ½ quantum spin liquid (QSL).

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Section: Resultssupporting

confidence: 74%

Heterospin frustration in a metal-fullerene-bonded semiconductive antiferromagnet

et al. 2022

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“…Similar Li + -ion arrangements are also observed in the other forms of Li + @C60 salts. 34,35 The inner Li + ion coordinates with the six-carbon ring with Li-C bond lengths in the range of 2.246-2.368 Å, which are consistent with the reported results. 36,5 The encapsulated Li + ions should strengthen the  back-bonding from the transition-metal centre to the fullerene cage; 5 however, the Cu ions do not coordinate with the rings of the six-carbon (pink atoms in Figure 1b) owing to the highly symmetrical array of the four Cu ions.…”

Section: Metalsupporting

confidence: 91%

S = ½ Heterospin Frustration in a Metal‒Fullerene-Bonded Semiconductive Antiferromagnet

Yongbing¹,

Cui²,

Takaishi³

et al. 2021

Preprint

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Lithium-ion-encapsulated fullerenes (Li+@C60) are 3D superatoms with rich oxidative states. However, no current studies have reported Li+@C60 as ligands. Here, we report a conductive and magnetically frustrated metal–fullerene-bonded framework {[Cu4(Li+@C60)(L)(py)4](NTf2)(hexane)n (1) prepared from redox-active dinuclear metal complex Cu2(L)(py)4 and lithium-ion-encapsulated fullerene salt (Li+@C60)(NTf2−), where ligand L denotes 1,2,4,5-tetrakis(methanesulfonamido)benzene, py pyridine, and NTf2− the bis(trifluoromethane)sulfonamide anion. Electron donor Cu2(L)(py)2 bonds to acceptor Li+@C60 via eight Cu‒C bonds. Cu–C bond formation stems from spontaneous charge transfer (CT) between Cu2(L)(py)4 and (Li+@C60)(NTf2−) by removing the two-terminal py molecules, yielding triplet ground state [Cu2(L)(py)2]+(Li+@C•‒ 60), evidenced by absorption and electron paramagnetic resonance (EPR) spectra, magnetic properties, and quantum chemical calculations. Moreover, Li+@C•‒ 60 radicals (S = ½) and Cu2+ ions (S = ½) interact antiferromagnetically in triangular spin lattices in the absence of long-range magnetic ordering up to 1.8 K; thus, compound 1 is a potential candidate for an S = ½ quantum spin liquid.

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“…Previous studies demonstrate that provided the dipole cannot reorient fast enough in composites, this causes the dielectric constant to decrease 72 . Others propose that the low dielectric constant of organic photovoltaics assists the exciton to present at larger distances 73 .…”

Section: Resultsmentioning

confidence: 99%

C70 Fullerene Cage as a Novel Catalyst for Efficient Proton Transfer Reactions between Small Molecules: A Theoretical study

Varadwaj

Marques

2019

Sci Rep

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When acids are supplied with an excess electron (or placed in an Ar or the more polarizable N 2 matrix) in the presence of species such as NH 3 , the formation of ion-pairs is a likely outcome. Using density functional theory and first-principles calculations, however, we show that, without supplying an external electron or an electric field, or introducing photo-excitation and -ionization, a single molecule of HCl or HBr in the presence of a single molecule of water inside a C 70 fullerene cage is susceptible to cleavage of the σ-bond of the Brønsted-Lowry acid into X − and H + ions, with concomitant transfer of the proton along the reaction coordinate. This leads to the formation of an X − ··· + HOH 2 (X = Cl, Br) conjugate acid-base ion-pair, similar to the structure in water of a Zundel ion. This process is unlikely to occur in other fullerene derivatives in the presence of H 2 O without significantly affecting the geometry of the carbon cage, suggesting that the interior of C 70 is an ideal catalytic platform for proton transfer reactions and the design of related novel materials. By contrast, when a single molecule of HF is reacted with a single molecule of H 2 O inside the C 70 cage, partial proton transfers from HF to H 2 O is an immediate consequence, as recently observed experimentally. The geometrical, energetic, electron density, orbital, optoelectronic and vibrational characteristics supporting these observations are presented. In contrast with the views that have been advanced in several recent studies, we show that the encaged species experiences significant non-covalent interaction with the interior of the cage. We also show that the inability of current experiments to detect many infrared active vibrational bands of the endo species in these systems is likely to be a consequence of the substantial electrostatic screening effect of the cage.

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

Cited by 17 publications

References 37 publications

Heterospin frustration in a metal-fullerene-bonded semiconductive antiferromagnet

Heterospin frustration in a metal-fullerene-bonded semiconductive antiferromagnet

S = ½ Heterospin Frustration in a Metal‒Fullerene-Bonded Semiconductive Antiferromagnet

C70 Fullerene Cage as a Novel Catalyst for Efficient Proton Transfer Reactions between Small Molecules: A Theoretical study

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