Photochemical Orifice Expansion of a Cage-Opened C<sub>60</sub> Derivative

Hashikawa, Yoshifumi; Hasegawa, Shota; Murata, Yasujiro

doi:10.1021/acs.orglett.1c00990

Cited by 12 publications

(4 citation statements)

References 38 publications

(26 reference statements)

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“…The distance between the Ar and the closest hydroxy oxygen was measured to be 4.113(5) Å, which is apparently larger than the sum of van der Waals radii (3.40 Å) [19] . On the contrary, 16 short contacts were detected between the Ar and the caged carbon with an averaged distance of 3.49 Å (Figure S5), which is similar to the previously reported Ar@open‐C 60 (3.50 Å) [17c] . These results further support that the hydroxy groups have negligible interactions with the Ar atom on the ground state structure.…”

Section: Resultssupporting

confidence: 86%

Synthesis of an Open‐Cage C₆₀ Derivative with a Double Stopper

Huang,

Hashikawa,

Murata

2023

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The construction of a suitable stopper on a C60 orifice is of importance to prevent the release of once‐encapsulated chemical species. However, a single stopper on a large orifice is in usual not sufficient to retain a small molecule within the C60 cavity. In this work, we introduced a double stopper, constituted of two hydroxy groups, on a huge orifice with a ring‐atom count of 18 by a reduction using BH3⋅THF. The resulting double stopper was demonstrated to effectively isolate an argon atom inside the cavity so that the argon was retained even under mass spectrometric conditions at 200 °C. The structure of the open‐cage C60 derivative with the double stopper was confirmed by X‐ray diffraction analysis, showing a dimeric configuration via intermolecular hydrogen‐bondings. The dimerization behavior was also studied in solution.

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Section: Resultssupporting

confidence: 86%

Synthesis of an Open‐Cage C₆₀ Derivative with a Double Stopper

Huang,

Hashikawa,

Murata

2023

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“…According to theoretical calculations [B3LYP/6-31G(d) (Figure 3b)], the methylene protons are shielded by the aniline ring that faces the quinoxaline unit, thus observing the higher field shifts. Though the aniline ring seems to cover the 20-membered-ring orifice, the encapsulated H 2 O molecule was detected as a severely broadened signal at δ −10.73 ppm, indicating the flexibility of the aniline ring as a dynamic stopper, 19 which allows the H 2 O molecule to undergo the insertion/escape equilibrium faster than the NMR time scale.…”

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confidence: 99%

Amino-Functionalized Cage-Opened C₆₀ Derivatives

2021

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The amino-functionalized cage-opened [60]fullerene derivatives were synthesized by reactions with phenylenediamine. In this reaction, the diamine undergoes direct addition to the α,β-unsaturated carbonyl moiety. Further C−C bond scission is promoted by the intramolecular S N 2 reaction. These amino-functionalized derivatives possess high-lying highest occupied molecular orbital levels as suggested by electrochemical analyses. These compounds showed intense near-infrared absorption bands that tail to 900 nm, reflecting the optical transition with π−π* and charge transfer character.

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“…Note that the synthesis was performed under an inert Ar atmosphere. Though we could not observe a molecular ion peak corresponding to Ar@ 2 , open-[60]fullerene 2 should encapsulate an Ar atom upon considering the 1 H NMR spectral feature similar to that of 6 . The larger orifice of 2 relative to that of 6 might allow a once-encapsulated Ar atom to escape under the measured conditions.…”

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confidence: 99%