Radical Reactivity of Aza[60]fullerene: Preparation of Monoadducts and Limitations

Abstract

Six aza[60]fullerene monoadducts were synthesized by the thermal reaction between the azafullerene radical C(59)N* and 9-alkyl-substituted fluorenes, 9,10-dihydroanthracene, or xanthene. Unlike fluorenes, dihydroanthracene, and xanthene, the structurally related substituted diphenylmethanes, ethylbenzene, cumene, 1,2-diphenylethane, 5,6,11,12-tetrahydrodibenzo[a,e]cyclooctene, 10,11-dihydro-5H-dibenzo[a,d]cycloheptene, 9-methylanthracene, and 9-benzylanthracene do not lead to the isolation of azafullerene monoadducts. Moreover, 1,2-dichlorobenzene, the most commonly utilized solvent for azafullerene reactions, reacts slowly with the azafullerenyl radical C(59)N* affording the corresponding aza[60]fullerene monoadduct.

Azafullerene C59N in Donor–Acceptor Dyads: Synthetic Approaches and Properties

“…Heating N ‐MEM‐[60]ketolactam in degassed o ‐dichlorobenzene ( o DCB) in the presence of p ‐toluenesulfonic acid ( p TsOH) yields (C 59 N) 2 in high yield. In all, the total yield from C 60 is around 10 % (20 % based on recovered C 60 ) …”

Conformationally Restricted Triarylmethanes: Synthesis, Photophysical Studies, and Applications

“…[13,14] Bridging the two aryl rings with heteroatoms or through bonds and/or introducing bulky substituents as shown in (Figure 2.) The nonfluxional structure of these molecules result in more natural abstraction of the corresponding methine hydrogen, faster generation of the corresponding free radicals [17] making it highly intriguing chemistry of these types of molecules. [16] Hence these molecules can be termed as "conformationally restricted" (CRT) analogues of triarylmethanes.…”

ChemInform Abstract: Azafullerene C59N in Donor—Acceptor Dyads: Synthetic Approaches and Properties

“…In all, the total yield from C 60 is around 10 %( 20 %b ased on recovered C 60 ). [5] Azafullerened erivatives stem from either (C 59 N) 2 or,i ns ome cases, N-MEM-[60]ketolactam. [2a] As shown in Scheme 2, heating as olution of either of the aforementioned compounds in oDCB in the presense of oxygen (air flow), pTs OH anda na ppropriate nucleophile NuH, resultsi nt he azafullerene derivative 3.M echanistically,( C 59 N) 2 undergoes homolytic cleavage on heating to give radical 1,w hich gets oxidized to cation 2.…”