Inhibition of the formation and decay of stilbene core radical cations by the dendron during the photoinduced electron transfer.

Formation and decay processes of stilbene core radical cation (ST*+) during the photoinduced electron transfer have been studied for a series of stilbene bearing benzyl ether-type dendrons (D). ST*+ and the radical cation of peripheral dendron (D*+) were generated by intermolecular hole transfer from biphenyl radical cation, which was generated from photoinduced electron transfer from biphenyl to the singlet-excited 9,10-dicyanoanthracene in a mixture of acetonitrile and 1,2-dichloroethane (3:1). An intramolecular dimer radical cation of benzyl groups at the terminal of stilbene dendrimer was indicated as a hole trapping site. Subsequent hole transfer from the trapping site to the core ST generated ST*+. The shielding effects of D depending on the dendrimer generation on the growth and decay of ST*+ were observed. It was revealed for the first time that D acts as the hole trapping site and the hole conductor on the way of the exothermic hole transfer from the terminal of D to the central core ST. We also found that D inhibits the charge recombination with 9,10-dicyanoanthracene radical anion because of the steric hindrance.

Effects of benzyl ether type dendrons as hole-harvesting antennas, and shielding for the neutralization of stilbene core radical cations with chloride ion during two-photon ionization of stilbene dendrimers having stilbene core and benzyl ether type dendrons.

The two-photon ionization (TPI) process (308 and 266 nm) of stilbene dendrimers having a stilbene core and benzyl ether type dendrons has been investigated in an acetonitrile and 1,2-dichloroethane mixture (3:1) in order to elucidate the dendrimer effects. The quantum yield of the formation of stilbene core radical cation during the 308-nm TPI was independent of the dendron generation of the dendrimers, whereas a generation dependence of the quantum yield of the radical cation was observed during the 266-nm TPI, where both the stilbene core and benzyl ether type dendron were ionized, suggesting that the subsequent hole transfer occurs from the dendron to the stilbene core, and that the dendron acts as a hole-harvesting antenna. The neutralization rate of the stilbene core radical cation with the chloride ion, generated from the dissociative electron capture by 1,2-dichloroethane, decreased with the increase in the dendrimer generation, suggesting that the dendron is an effective shield of the stilbene core radical cation against the chloride ion.

Synthesis and isomerization of azobenzene dendrimers.

3,3',5,5'-Tetramethoxyazobenzene and related meta-substituted azobenzene dendrimers show the first evidence of the dendritic effect on trans-to-cis photoisomerization; the thermodynamic parameters for cis-to-trans isomerization have been determined.

1,3,5-tristyrylbenzene dendrimers: a novel model system to explore oxygen quenching in a highly organized environment.

Control of the efficiency of photoisomerization by oxygen was demonstrated for 1,3,5-tristyrylbenzene dendrimers 1-3; the large dendrons do not significantly affect the photochemistry itself due to volume-conserving isomerization mechanisms but may affect the mobility of the molecules.

Photoisomerization of stilbene dendrimers: the need for a volume-conserving isomerization mechanisms.

Highly branched stilbene dendrimers were synthesized and their photochemical behavior was studied. Even the stilbene dendrimer with molecular weight over 6500 underwent trans-cis isomerization in the excited singlet state within the lifetime of 10 ns. The photoisomerization of C=C double bond of stilbene dendrimers in the excited state may proceed by a volume-conserving novel mechanism such as hula-twist rather than conventional 180 degrees rotation around the C=C double bond based on fluorescence and isomerization experiments.