Unraveling the Nature and Strength of Non‐Covalent Interactions on the Surface of Fullerenes

Yamada, Michio

doi:10.1002/cplu.202300062

Cited by 7 publications

(5 citation statements)

References 81 publications

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“…The use of fullerenes in catalysis is surprisingly underdeveloped [45][46][47][48][49][50][51]. Anion-π and cation-π interactions on fullerenes attract similarly little attention until today [52][53][54][55][56][57]. Anion-π catalysis on fullerenes has been introduced in 2017 [12].…”

Section: Review Anion-π Catalysis On Fullerenesmentioning

confidence: 99%

Anion–π catalysis on carbon allotropes

Gutiérrez López,

Tan,

Renno

et al. 2023

Beilstein J. Org. Chem.

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Anion–π catalysis, introduced in 2013, stands for the stabilization of anionic transition states on π-acidic aromatic surfaces. Anion–π catalysis on carbon allotropes is particularly attractive because high polarizability promises access to really strong anion–π interactions. With these expectations, anion–π catalysis on fullerenes has been introduced in 2017, followed by carbon nanotubes in 2019. Consistent with expectations from theory, anion–π catalysis on carbon allotropes generally increases with polarizability. Realized examples reach from enolate addition chemistry to asymmetric Diels–Alder reactions and autocatalytic ether cyclizations. Currently, anion–π catalysis on carbon allotropes gains momentum because the combination with electric-field-assisted catalysis promises transformative impact on organic synthesis.

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Section: Review Anion-π Catalysis On Fullerenesmentioning

confidence: 99%

Anion–π catalysis on carbon allotropes

Gutiérrez López,

Tan,

Renno

et al. 2023

Beilstein J. Org. Chem.

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“…Noncovalent interactions (NCIs), despite being generally rather weak, dictate the properties of many molecular systems and their response to environmental perturbations, playing a fundamental role in chemistry, biology and materials science. Not surprisingly, they receive increasing attention in many different fields, such as supramolecular chemistry and catalysis, [1][2][3] new functional materials, 4 polymers, 5 surface phenomena, [6][7][8] molecular sensors, 9,10 or biochemistry, [11][12][13][14][15] just to cite a few of the most recent contributions in different areas.…”

Section: Introductionmentioning

confidence: 99%

Discovering trends in the Lewis acidity of beryllium and magnesium hydrides and fluorides with increasing clusters size

Mó,

Montero‐Campillo,

Yáñez

et al. 2024

J Comput Chem

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We have reported in the last years the strong effect that Be‐ and Mg‐containing Lewis acids have on the intrinsic properties of typical bases, which become acids upon complexation. In an effort to investigate these changes when the Be and Mg derivatives form clusters of increasing size, we have examined the behavior of the (MX2)n (M = Be, Mg; X = H, F; n = 1, 2, 3) clusters when they interact with ammonia, methanimine, hydrogen cyanide and pyridine, and with their corresponding deprotonated forms. The complexes obtained at the M06‐2X/aug‐cc‐pVTZ level were analyzed using the MBIE energy decomposition formalism, in parallel with QTAIM, ELF, NCIPLOT and AdNDP analyses of their electron density. For n = 1 the interaction enthalpy for the different families of monomers, Be (Mg) hydrides and Be (Mg) fluorides, follows the same trend as the intrinsic basicity of the base that interacts with them. This interaction is greatly reinforced after the deprotonation of the base, resulting in a significant enhancement of the intrinsic acidity of the corresponding MX2–Base complex. For (MX2)2 clusters a further reinforcement of the interaction with the base is observed, this reinforcement being again larger for the deprotonated complexes. However, the concomitant increase of their intrinsic acidity is one order of magnitude larger for hydrides than for fluorides. Unexpectedly, the cyclic conformers (MX2)3, which are more unstable than the linear ones, become the global minima after association with the base and the same is true for the deprotonated complex. Accordingly, a further increase of the intrinsic acidity of the (MX2)3–Base complexes with respect to the (MX2)2–Base ones is observed. This effect is maximum for (MgF2)3 clusters, to the point that the (MgF2)3–Base complexes become more acidic than nitric acid, the extreme case being the cluster (MgF2)3–NCH, whose acidity is higher than that of perchloric acid.

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“…Furthermore, we measured anionic arene–fullerene interactions, [9] which have not yet been elucidated, by converting a torsion balance bearing a 4‐hydroxyphenyl group to the corresponding phenolate anion. At this point, the electrostatic potential surface of fullerenes is considered to be predominantly positive, contrary to that of benzene [3f,6c] . Therefore, anions are expected to interact more strongly with fullerenes than cations.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Conformational Analysis of Fullerene Torsion Balances for Assessing the Contribution of Dispersion and Anionic Character in Non‐Covalent Arene–Fullerene Interactions

Yamada

Sahara

Koizumi

et al. 2023

Chemistry A European J

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We employ a molecular torsion balance displaying bifurcated conformational isomerism to quantitatively evaluate the non‐covalent interactions between the fullerene surface and substituted arene moieties containing elements with high atomic numbers, as well as the thermodynamic processes involved in the folding equilibrium using nuclear magnetic resonance spectroscopy. The interaction between fullerene and haloaryl groups was stronger in cases where the introduced halogen had a higher atomic number, indicating that dispersion forces play a significant role in the interaction between fullerenes and 4‐haloaryl groups. The dispersion term also significantly contributed to the interaction between fullerene and the 4‐mercaptophenyl group. Moreover, the addition of an appropriate base to the 4‐mercaptophenyl‐appended torsion balance formed the corresponding thiophenolate anion, resulting in a large negative change in the folding free energy in CDCl3. Detailed analysis suggested that the observed attractive anionic arene–fullerene interactions predominantly originated from solvation effects.

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Unraveling the Nature and Strength of Non‐Covalent Interactions on the Surface of Fullerenes

Cited by 7 publications

References 81 publications

Anion–π catalysis on carbon allotropes

Anion–π catalysis on carbon allotropes

Discovering trends in the Lewis acidity of beryllium and magnesium hydrides and fluorides with increasing clusters size

Synthesis and Conformational Analysis of Fullerene Torsion Balances for Assessing the Contribution of Dispersion and Anionic Character in Non‐Covalent Arene–Fullerene Interactions

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