Supramolecular Fullerene Chemistry: A Comprehensive Study of Cyclophane‐Type Mono‐ and Bis‐Crown Ether Conjugates of C₇₀.

Tether‐Directed Remote Functionalization of Fullerenes C60 and C70

“…In the chemistry of C 70 , the tether-based methodology has provided access to only a few functionalization patterns, albeit with good regio-and stereoselectivities [36][37][38]. As to the spacer-controlled multifunctionalization of other higher fullerenes, it remains a terra incognita.…”

“…These first-observed cases of cation-complexation-induced alterations of the redox potentials of fullerene derivatives are due to an electrostatic effect of the K + ion fixed in close proximity of the carbon spheroid. The measured shift is particularly large for (±)-17a and (±)-17b (+170 mV, 0/-1 redox couple) in which cases the fullerene is sandwiched between two cations [37,38]. Incorporation of C 60 derivative (±)-14 in the membrane of an ion-selective electrode showed that K + forms the strongest complex among the alkali metal ions [34,35].…”

“…Dibenzo [18]crown-6-derived bismalonates were also successfully used in the first tether-directed remote functionalization of C 70 [36][37][38]. Macrocyclization of this fullerene with bismalonate 13 afforded four stereoisomers, namely racemates (±)-16a and (±)-16b, with complete regioselectivity (Scheme 4) [36,38].…”

“…When bisadducts (±)-16a and (±)-16b were allowed to separately react with syn-disubstituted dibenzo [18]crown-6 derivative 15, tetrakisadducts (±)-17a and (±)-17b, respectively, with C 70 sandwiched between two crown ethers, were obtained regio-and stereoselectively [37,38]. It should be pointed out that the syn substitu-Scheme 5.…”

Two-component polymer films of palladium and fullerene with covalently linked crown ether voids: effect of cation binding on the redox behavior

“…For example, a series of fulleropyrrolidine derivatives were synthesized by 1,3-dipolar cycloaddition to C 60 [1][2][3][4][5][6][7][8][9][10]. This procedure has been used to link a crown ether moiety to fulleropyrrolidine [11][12][13][14][15][16][17][18][19][20][21]. It was shown [11][12][13][14]21] that crown ether-bearing fulleropyrrolidine possesses interesting electrochemical and photophysical properties.…”