Nonclassical Abramov Products Formed on Orifices of Cage‐Opened C<sub>60</sub>Derivatives

Hashikawa, Yoshifumi; Okamoto, Shu; Murata, Yasujiro

doi:10.1002/chem.202004035

Cited by 16 publications

(5 citation statements)

References 47 publications

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“…In 2012, Gan and co-workers pronounced that a cage-opened C 60 derivative having an enamine moiety showed an intense green color in solution with the longest absorption band tailing to 850 nm (Figure ). Compared with π-extended cage-opened C 60 derivatives showing an intense near-infrared (NIR) absorption, amino functionalization seems to be a promising strategy for readily preparing fullerene-based NIR dyes as in the case of phosphorus functionalization . Because of multiple functional groups on the rims of orifices, amines often undergo nucleophilic addition to olefins and/or carbonyl groups though the detailed reaction mechanism remains unclear .…”

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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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Amino-Functionalized Cage-Opened C₆₀ Derivatives

2021

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“…(a) MO energy levels with optical transitions (TD M06-2X using LanL2DZ (metals) and 6-31G(d,p) (the rest), SMD model in PhCl). The transition energies were calibrated by a factor of 0.72 . (b) Selected MOs of 1 Rh .…”

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π-Backbonding on Group 9 Metal Complexes Bearing an η²-(H₂O@C₆₀) Ligand

2022

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As a measure of d-π* back-donation, IR stretching modes are, in general, used for metal carbonyl compounds. Once the ligand is replaced with olefins (metal−arene complexes), it can be analyzed crystallographically unless otherwise the C−C bond length falls into values within standard deviation. Herein, we propose a novel measure using an η 2 -(H 2 O@C 60 ) ligand in group 9 metal− fullerene complexes, in which the stronger d-π* backbonding causes enhanced sp 3character on the coordinated olefinic bond and consequently leads to the restricted rotation for the H 2 O molecule as detectable by the 1 H NMR relaxation time. The π-backbonding strengths were, therefore, found to follow the ascending order of atomic numbers (Co < Rh < Ir) in CpM(CO)(η 2 -H 2 O@C 60 ) (Cp = cyclopentadienyl), associated with the anodic shift on oxidation potentials and hypsochromic shift on absorption edges.

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“…1). The nucleophilic addition of Grignard reagents 13 as well as phosphites 10,12 c ,14 and phosphines 15 was also proven to be applicable. Recently, we reported the pressure-induced dehydroxyhydrogenation of an open-cage bis(hemiketal) derivative of C 60 by the use of Li + [B(C 6 F 5 ) 4 ] − ·2.5Et 2 O in which actual active species might be B(C 6 F 5 ) 3 ˙ − or [HB(C 6 F 5 ) x R 3− x ] − (R = OH or OEt) formed via hydrolysis.…”

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