On the Polarity of Buckminsterfullerene with a Water Molecule Inside

Ensing, Bernd; Costanzo, Francesca; Silvestrelli, Pier Luigi

doi:10.1021/jp311161q

Cited by 44 publications

(58 citation statements)

References 21 publications

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“…42,43 Calculations and measurements on H 2 O@C 60 give similar results. 13,26,44 Conclusion In summary we have synthesized the endohedral fullerene HF@C 60 and characterized it by solution and solid-state NMR spectroscopy, observing the large 1 J HF coupling indicative of an isolated molecule. Electrochemical studies and UV-spectroscopy show that the endohedral molecule has no detectable effect on the electronic structure of the cage.…”

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confidence: 92%

The dipolar endofullerene HF@C60

et al. 2016

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Abstract:The cavity inside fullerenes provides a unique environment for the study of isolated atoms and molecules. We report encapsulation of hydrogen fluoride inside C 60 using molecular surgery to give the endohedral fullerene HF@C 60 . The key synthetic step is the closure of the open fullerene cage while minimizing escape of HF. The encapsulated HF molecule moves freely inside the cage and exhibits quantization of its translational and rotational degrees of freedom, as revealed by inelastic neutron scattering and infrared spectroscopy. The rotational and vibrational constants of the encapsulated HF molecules were found to be redshifted relative to free HF. The NMR spectra display a large 1 H-19 F Jcoupling typical of an isolated species. The dipole moment of HF@C 60 was estimated from the temperature-dependence of the dielectric constant at cryogenic temperatures and showed that the cage shields around 75% of the HF dipole.Molecular endofullerenes consist of fullerene cages encapsulating small molecules, which are free to rotate and translate inside the cage. 1 The dihydrogen and water endofullerenes H 2 @C 60 , H 2 O@C 60 , and their isotopologues, have been synthesized by the procedure known as 'molecular surgery', in which synthetic operations are used to open a hole in the fullerene allowing encapsulation of the guest, followed by a suturing technique to reform the pristine fullerene shell. [2][3][4] Recently the approach has been extended to C 70 and C 59 N. [5][6][7] The confined molecules display quantization of their coupled translational and rotational degrees of freedom, and exhibit phenomena such as nuclear spin isomerism and orthopara conversion. [8][9][10][11][12] Recently it was shown that nuclear spin conversion of the encapsulated water molecules in H 2 O@C 60 leads to a change in the dielectric constant of the material. 13 One system of great interest is HF@C 60 , in which each fullerene cage contains a single hydrogen fluoride (HF) molecule. This material offers the possibility to study the spectroscopic properties of nearisolated and freely rotating HF molecules under a wide range of conditions, free from the complications of dimerization and hydrogen bonding. Predictions of the properties of HF@C 60 have been made using classical, 14 semiempirical 15,16 and quantum chemistry techniques. [17][18][19][20] Furthermore it has been postulated that endofullerenes containing freely rotating electric dipoles could exhibit ferroelectricity, due to cooperative alignment of the interacting electric dipole moments. 21 2The first examples of open-cage endofullerenes encapsulating a hydrogen fluoride molecule have recently appeared, including HF@1. 22,23 Herein we report the successful suturing of HF@1 to give the closed-cage species HF@C 60 . We present NMR, infrared, and neutron scattering data on HF@C 60 which show that the translational and rotational motions of the HF molecule inside the cage are quantized. Interactions with the cage modify the rotational and vibrational constants of the encapsula...

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The dipolar endofullerene HF@C60

et al. 2016

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“…The encapsulated water molecule was modeled by the flexible SPC/E model. Since there is only nonbond interatomic interaction between water molecule and carbon atoms, 23 method is applied to form a constant heat flow (q) from the hot reservoir to cold reservoir along the z-direction by rescaling the velocity of the atoms in both reservoirs. 37 All simulations were performed by using LAMMPS.…”

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confidence: 99%

Probing Thermal Conductivity of Fullerene C₆₀ Hosting a Single Water Molecule

Gao

2015

J. Phys. Chem. C

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Encapsulation of a single water molecule inside the fullerene C 60 can yield a significant change on its fundamental properties. Through comprehensive reverse nonequilibrium molecular dynamics (RNEMD) simulations, we investigate the thermal conductivity of endohedral C 60 fullerene containing a single water molecule. The encapsulated single water molecule enhances the thermal phonon propagation resistance of the fullerene C 60 due to its interaction with carbon atoms, and brings down the thermal conductivity of the fullerene C 60 . Further simulations indicate that the thermal conductivity will depend on the external electrical field due to the polarity of the encapsulated water molecule. A larger electrical intensity will lead to a smaller thermal conductivity. A hierarchical model is proposed to quantitatively understand thermal behavior of the single endohedral fullerene and its enabled single-chain structures, and shows good agreement with simulations.

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“…Inside the cages, these molecules are expected to exhibit unusual physical properties that are absent in their isolated form because of the interaction between the encapsulated molecules and the fullerene cages [16,17], as in the case of encapsulated molecules inside carbon nanotubes. In addition to water encapsulation in fullerenes, water molecules have also been encapsulated in the C 60 dimer [18], which is two C 60 molecules connected via [2 + 2] cycloaddition [19], as in the case of C 60 polymers [20][21][22][23][24].…”

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confidence: 99%

An anomalous dipole–dipole arrangement of water molecules encapsulated into C60 dimer

Nomura

Okada

2014

Chemical Physics Letters

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a b s t r a c tBased on first-principles total energy calculations, we demonstrate that two water molecules encapsulated in the C 60 dimer form a peculiar tail-to-tail dipole arrangement that is energetically unfavorable in classical electrodynamics. This arrangement is ascribed to charge depression at the wall of C 60 associated with [2 + 2] cycloaddition in the dimer structure resulting in a decrease of the energy cost of Coulomb repulsive interaction in the arrangement. First-principles molecular dynamics simulations also show that the water molecules retain the peculiar arrangement up to the temperature of about 10 K.

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On the Polarity of Buckminsterfullerene with a Water Molecule Inside

Cited by 44 publications

References 21 publications

The dipolar endofullerene HF@C60

The dipolar endofullerene HF@C60

Probing Thermal Conductivity of Fullerene C₆₀ Hosting a Single Water Molecule

An anomalous dipole–dipole arrangement of water molecules encapsulated into C60 dimer

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On the Polarity of Buckminsterfullerene with a Water Molecule Inside

Cited by 44 publications

References 21 publications

The dipolar endofullerene HF@C60

The dipolar endofullerene HF@C60

Probing Thermal Conductivity of Fullerene C60 Hosting a Single Water Molecule

An anomalous dipole–dipole arrangement of water molecules encapsulated into C60 dimer

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Probing Thermal Conductivity of Fullerene C₆₀ Hosting a Single Water Molecule