Mono-and multiple-functionalized C 60 derivatives were synthesized and studied for their photophysical properties. Electronic absorption spectra and absorptivities of the C 60 derivatives in solution were measured and compared. By recording the fluorescence spectra using a near-infrared-sensitive emission spectrometer, we quantitatively determined fluorescence quantum yields of the C 60 derivatives. For the mono-functionalized C 60 derivatives, the compound with a [5,6]-open fulleroid addition pattern on the fullerene cage appeared to be considerably less fluorescent than those with a [6,6]-closed cage addition pattern. Despite the disturbance of the electronic structure via multiple additions to the fullerene cage, the multiple-functionalized C 60 derivatives exhibited no dramatic changes in fluorescence quantum yields in comparison with the mono-functionalized C 60 derivatives. The fluorescence lifetimes of the C 60 derivatives, obtained using the time-correlated single photon-counting technique, were all in the range of 1-3 ns. In addition, the dependencies of the fluorescence intensities and lifetimes of the C 60 derivatives on the concentration of the quencher N,N-diethylaniline (DEA) were evaluated. Apparently, upon photoexcitation, even the C 60 derivatives with a hexa-functionalized fullerene cage underwent significant electron-transfer interactions with the electron donor DEA, resulting in efficient fluorescence quenching. In a polar solvent, the contribution of static quenching also became important. The results for different derivatives and their molecular structural and mechanistic significance are discussed.

The condensation between dienophiles and α,β-unsaturated hydrazone azadienes was previously reported to afford piperidines. During an attempt to adapt this reaction to the preparation of piperidine-based conformationally-restricted analogs of glutamate, it was discovered that the electrophile, dimethyl oxoglutaconate (DOG) led to highly substituted dihydropyrans in 20–50% yield. The unexpected pyran product likely results from an initial 1,4-addition of the hydrazone to the oxoglutaconate followed by intramolecular cyclization of the resultant enolate oxygen to the α,β-unsaturated iminium ion. Further manipulations afford substituted tetrahydropyran 6-methamino-2,4-dicarboxylic acids.