A series of 1,3,5-phenylene-based rigid dendritic porphyrins were synthesiz
ed by Suzuki coupling between a porphyrin core and dendron units. The intra
molecular energy transfer was studied by absorption and fluorescence spectr
oscopies. The encapsulation of the porphyrin core within the 1,3,5-phenylen
e dendron units was found to provide highly efficient energy transfer from
the dendron units to the porphyrin core. The dendritic wedge structure affe
cted the energy transfer efficiency. The 1,3,5-phenylene-based rigid dendro
n units act as highly efficient light-harvesting antennae. These dendritic
porphyrins have also been examined as C-60 hosts and substrate-selective ox
idation catalysts. The attachment of the second generation of 1,3,5-phenyle
ne-based dendron units with the porphyrin core enabled a stable inclusion o
f C60 in toluene. Furthermore, the size and shape of the nanospace in the r
igid dendritic porphyrins were found to affect the selectivity of substrate
s in the catalytic olefin oxidations.