Reaction of fullerenes and benzyne

Theoretical estimation of the rate of photoinduced charge transfer reactions in triphenylamine C60 donor–acceptor conjugate

“…[31,33] On the other hand, C60 is an excellent electron donor [35][36][37][38] that can react with a variety of chemical agents. [39][40][41][42][43][44] Recently, based on electrochemical and photophysical studies, Echegoyen et al [45] determined kct for the TPA-C60 and TPA-Sc3N@Ih-C80 donor-acceptor conjugates and showed that (i) ultrafast charge separation (CS) reactions occur at the molecular interface, thus giving evidence of CT activity; (ii) TPA-Sc3N@Ih-C80 generates longer-lived photoinduced charge transfer states (CTSs) than does TPA-C60; (iii) increasing the distance of the donor-acceptor interface produces longer-lived CTSs; (iv) nonpolar solvents bring about lack of CT activity; on the contrary, more polar solvents can slow down the charge recombination (CR) reaction; (v) a smaller value of kct for the CR reaction with Sc3N@Ih-C80 in comparison with C60 was found, which was attributed to a smaller value of the driving force.…”

Thermal [2+2] Intramolecular Cycloadditions of Fuller‐1,6‐enynes

“…[5] Furthermore, cyclobutene 8 has recently been isolated as a stable and well-characterized silane derivative. [6] Recently, we reported that 1,6-enynes in which fullerene C 60 was used as the alkene component (fuller-1,6-enynes) undergo a highly efficient and regioselective [2+2+1] intramolecular Pauson-Khand reaction with [Co(CO) 8 ] to form a new type of fullerene derivative with an unprecedented three or five fused pentagonal rings on the fullerene surface.…”

“…Hoke et al first reported that benzene reacted with C 60 to give a series of [2+2] cycloadducts, from which the monoadduct was isolated and characterized. [8] Since then, other photochemical [2+2] cycloadditions of fullerenes have been reported. [9] The synthesis of the starting fuller-1,6-enynes 10 a-e was carried out by 1,3-dipolar cycloaddition reaction of the azomethine ylides, which were generated in situ from propargyl-containing glycine derivatives [10] 9 a-e and formaldehyde, to [60]fullerene in refluxing chlorobenzene for 1 h following Pratos procedure.…”

“…Figure 2. Optimized transition-state structure (ONIOM(UB3LYP/6-31G*:UAM1)) with the most relevant bond lengths [] and angles [8]. Darkened atoms constitute the model system treated at high level in the ONIOM approach.…”

Perchloropyracylene and its Fusion with C60 by Chlorine‐Assisted Radio‐Frequency Furnace Synthesis

“…[72] Commonly photoexcitation is effective for this purpose, although examples of thermal excitation are known as well. [73][74][75] Therefore, mixtures of approximately equimolar amounts of C 60 and the corresponding perchlorinated hydrocarbon were subjected to either thermal or photoexcitation in different solvents (toluene, hexane, CS 2 ) as well as in the solid state (only for photoexcitation). However, under none of the conditions tried was the formation of the cross-monoadduct observed, not even after two weeks of UV irradiation.…”