The primary radical products, namely C60 *− and C70 *− which were formed by reactions with either the solvated electrons or (CH3)2 *C(OH) radicals exhibit distinct absorption bands in the near-IR. Reaction of a water-soluble C60/γ-cyclodextrin complex with α-hydroxyalkyl radicals and hydrated electrons also involves electron transfer, as indicated by the dependence of the rate constants on the redox potential of the reducing species. Pulse radiolysis of micellar C60 solutions in BRIJ 35 and Triton X-100, on the other, exhibited electron transfer from various reducing radicals to the fullerence core. Water soluble fullerence mono-derivatives, e.g. C60[C(COO− 2]2 (1) and C60(C9H11O2)(COO−) (2) did not show any noticeable reactivity towards strongly reducing species which can be ascribed to the formation of clusters in which the hydrophobic fullerence core is shielded by a surrounding layer of negatively charged carboxylate functions. Upon incorporation into γ-cyclodextrin the reduction of 1 and 2 occurs rapidly as indicated by both an accelerated decay of the hydrated electron absorption and the formation of the characteristic near-IR absorption due to (C60 *−[C(COO−)/γ-CD and (C60 *−) (C9H11O2)(COO−)/γ-CD at 1030 nm. The all-equatorial bis- and tris-adducts, e.g. equatorial-C60[C(COO−)2]2 and equatorial-C60[C(COO−)2]3, did not show any evidence with respect to the occurrence of aggregation phenomena and yielded the respective radical anions equatorial-(C60 *−) [C(COO−)2]n in high yields.
Research on Chemical Intermediates – Springer Journals
Published: Apr 14, 2009
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