Design and synthesis toward starburst C[(sub)60]-based conducting polyanilines

Starburst C60-based hexanilino, hexa(dianilino), hexa(tetranilino), and hexa(hexadecaanilino)[60]fullerenes were prepared using monodisperse polynitrated C60, namely, hexanitro[60]fullerene 2 6 as a precursor mol­ ecule. A high yield of hexanitro[60]fullerene was obtained by the treatment of C6 0 molecules with gaseous nitrogen dioxide radicals at ambient tempera­ tures for more than 5 days. A shorter nitration period for the reaction resulted in a mixture of 26 and tetranitro[60]fullerenes 24. Formation of 24 followed a fast kinetic rate within 4h of reaction. Negative ion desorption chemical ionization mass spectra (DCF-MS) of both hexanilino[60]fullerene and hexanitroso [60] fullerene, a hydride-reduced product of 2 6, were utilized for substantiation of the number of nitro groups per C6 0 in 26. Detection of the molecular ion of C6 0 (NO ) 6 at mlz 901 can be correlated to the composi­ tion of its parent compound 2 6, as hexanitro[60]fullerenes containing 6 nitro addends per C6 0 cage. A fluorescence emission of hexa(tetranilino)fullerenes and hexa(hexadecaanilino)fullerenes centered at 415-418nm was attributed to the energy relaxation of oligoaniline arms, in its emeraldine base form, upon photo-excitation.