Dendrimers with a C60 core have been obtained by cyclization of dendritic bis-malonate derivatives at the carbon sphere. The resulting bis-methanofullerene derivatives have been characterised by electrospray (ES) and/or MALDI-TOF mass spectrometries. UVVIS absorption spectra, fluorescence spectra, and fullerene singlet excited state lifetimes have been determined in solvents of different polarity (toluene, dichloromethane, acetonitrile). These data suggest a tighter core/periphery contact upon increase of solvent polarity and dendrimer size. In all the investigated solvents, the fullerene triplet lifetimes are steadily increased with the dendrimer volume, reflecting lower diffusion rates of O2 inside the dendrimers along the series. Measurements of quantum yields of singlet oxygen sensitization indicate that longer lived triplet states generate lower amounts of singlet oxygen (1O2 ) in dichloromethane but not in apolar toluene suggesting a tighter contact between the dendritic branches and the fullerene core in CH2Cl2. In acetonitrile, the trend in singlet oxygen production is peculiar. Effectively, enhanced singlet oxygen production is monitored for the largest dendrimer. This reflects specific interactions of excited 1O2 molecules with the dendritic wedges, as probed by singlet oxygen lifetime measurements, possibly as a consequence of trapping effects.
A fullerene core to probe dendritic shielding effects
Accorsi G;Armaroli N;
2003
Abstract
Dendrimers with a C60 core have been obtained by cyclization of dendritic bis-malonate derivatives at the carbon sphere. The resulting bis-methanofullerene derivatives have been characterised by electrospray (ES) and/or MALDI-TOF mass spectrometries. UVVIS absorption spectra, fluorescence spectra, and fullerene singlet excited state lifetimes have been determined in solvents of different polarity (toluene, dichloromethane, acetonitrile). These data suggest a tighter core/periphery contact upon increase of solvent polarity and dendrimer size. In all the investigated solvents, the fullerene triplet lifetimes are steadily increased with the dendrimer volume, reflecting lower diffusion rates of O2 inside the dendrimers along the series. Measurements of quantum yields of singlet oxygen sensitization indicate that longer lived triplet states generate lower amounts of singlet oxygen (1O2 ) in dichloromethane but not in apolar toluene suggesting a tighter contact between the dendritic branches and the fullerene core in CH2Cl2. In acetonitrile, the trend in singlet oxygen production is peculiar. Effectively, enhanced singlet oxygen production is monitored for the largest dendrimer. This reflects specific interactions of excited 1O2 molecules with the dendritic wedges, as probed by singlet oxygen lifetime measurements, possibly as a consequence of trapping effects.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
