Electrochemical Evidence for Through‐Space Orbital Interactions in Spiromethanofullerenes

Abstract

tially separate components. The role of ion-molecule complexes has long been postulated in mass ~pectrometry,['~] but was based. in general. on indirect evidence from the fragmentation pattern of excited species from the ionization of molecules in which the putative components of the complex were initially covalently bound. In the specific case of alkylbenzenes. irrefutable mass spectrometric evidence is lacking for complexes such iis 2; results of molecular orbital ~alculations'~"~ do not appear inconsistent with ours.The gmcous s:iinpIc\ fix the radiolytic experimenls were prepared in se;iled 135 mL glass \cssels. iri-.idiatrd in a 220 Gainmacell (Nuclear Canada Ltd.). fitted with a thernio\tat. The gaseh and the chemicals used were research-grade products from coininti-cia1 source\. The radiolytic products were analyzed h) GC;MS (50 m long. 0.2 inin i . d fuxd d i c a column, coated with a 0.5 pm methylsilicons tilni: VG Micronia\?, TRIO quadrupolc mass spectrometer). The FT-ICR experiments were pcrlorinrd with .I Brukcr Spectrospin Apex TM 47e spectrometer equipped with a n exteriii ion miircc

[60]Fullerene as a Substituent

“…In spiromethanofullerenes, for instance, a similar effect has been called periconjugation. [25] Another example has been reported in the EPR study of radical anions of fulleropyrrolidine 4 by Brustolon and co-workers. [26] A further case of nitrogen lone pair delocalization into the fullerene core is that of fulleroproline 13 for which we measured the kinetic parameters of the trans 3 cis isomerization.…”

Multi‐Electron‐Acceptor Dyad and Triad Systems Based on Perylene Bisimides and Fullerenes

“…Both fullerenes and PTCDI-based species are an attractive target in forming multi-component acceptor-donor systems due to their extensive redox chemistry and photochemical properties. [4,[8][9][10][11][12][13][14] Fullerene absorbs light in the UV/Vis range [2] and PTCDI strongly absorbs light in the Vis/near IR range, [15,16] and both possess excellent electron-acceptor characteristics [17][18][19] and have been identified as candidates for the development of photovoltaic devices. [20][21][22] For such applications it is imperative that the electronic/redox and optical properties of the molecular species are fully understood.…”

Synthesis and electrochemical properties of fullerene-containing C60-acceptor dyads with fluoronitrobenzene and fluoroquinoxaline moieties as substituents

“…4 An analogous effect of the nitro group on the redox properties of the sphere was revealed in dinitro spirofluorenofullerene. 5 We also showed that the nitro pyrimidine fragment in azahomo[60]fullerene 6 and [60]fullereno[1´,2´:4,5]imidazo[1,2 b]pyrimidine 7 sub stantially increases the electron affinity of the fullerene sphere in these compounds.…”