Photoinduced inter- and intra-molecular electron transfer reactions of [60]fullerene and a tertiary amine. Formation of the cycloadduct N-ethyl-trans-2′,5′-dimethylpyrrolidino[3′,4′:1,2][60]fullerene

Abstract

The photoreduction of [60]fullerene by triethylamine results in the formation of a cycloadduct N-ethyl-trans-2',5'dimethylpyrrolidino[3',4': 1,21[60lfullerene, which is probably due to sequential intermolecular and intramolecular processes and argues strongly for the presence of ion pairs as intermediates in a room temperature toluene solution.

Regioselective Thermal Reaction between Triethylamine and C60 Revisited: X‐ray Confirmation of the Pentane‐Fused Adduct and in Situ Mechanism Study

“…Finally, the reaction mixture was subjected to HPLC separation which gave adduct 1 in 73 % yield based on consumed C 60 . The electronic configuration of 1 dissolved in toluene was investigated by UV/Vis spectroscopy (Figure 4), which is a simple method to determine the addition patterns of C 60 derivatives that may adopt either a [5,6]-or a [6,6]-structure. [11] According to the literature, the absorption peak at 432.6 nm is a strong evidence for the [6,6]-addition structure of 1.…”

“…The electronic configuration of 1 dissolved in toluene was investigated by UV/Vis spectroscopy (Figure 4), which is a simple method to determine the addition patterns of C 60 derivatives that may adopt either a [5,6]-or a [6,6]-structure. [11] According to the literature, the absorption peak at 432.6 nm is a strong evidence for the [6,6]-addition structure of 1. [11] Matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI/TOF MS) of 1 in a positiveion mode shows a molecular ion peak at m/z 848. onto the C 60 cage.…”

“…[5] The structure was presumed to be a pyrrolidino-C 60 cycloadduct (Figure 1, B). [6] Similarly, such pyrrolidino- Figure 1. Possible addition patterns of tertiary amines to C 60 .…”

Discrete Fulleride Anions and Fullerenium Cations

“…433 With triethylamine, a C-C bonded adduct can be trapped via subsequent intramolecular reactivity. 434 The photoinduced addition of ketene silyl acetals to 3 C 60 has been shown to proceed via C 60 -formation. 435 Subsequent radical coupling of the ion pair is believed to lead to C-C bond formation (Scheme 1), and similar reactivity is reported with allylic stannanes to add allylic groups to C 60 .…”

Effect of fullerenes on the structure and properties of linear and crosslinked polyesterurethane ureas

“…Tertiary aliphatic amines were soon thereafter shown to undergo photocycloadditions across them. 17 Despite the potentially rich chemistry available via reaction with aliphatic amines, a detailed understanding of the chemical and physical processes between them and fullerenes potentially influencing both chemical and super molecular structure of polymer composites was slow to develop. The nanoscale phase separation in polymer/fullerene bulk heterojunction composites requires the use of very sensitive new techniques for imaging, e.g., a highresolution transmission electron microscope together with selected area electron diffraction, to visualize the polymer and fullerene distributions and their amorphous or crystalline organization in the film.…”