A new approach to creating noncovalent charge transfer ensembles is described It is based on two components that are linked through anion-receptor interactions The first component is sapphyrin a pentapyrrolic expanded porphyrin, which is capable of carboxylate anion recognition and more importantly can act as a photodonor when irradiated in the presence of a suitable electron acceptor The second component is the electron acceptor and consists of one of two different C-60 fullerene cores functionalized with multiple carboxylate anion groups arranged in a dendritic fashion Depending on the specific choice of the fullerene carboxylate anion dendrimer employed in ensemble construction 1 1 or 1 2 complexes are formed when the C-60 cores are titrated with sapphyrin The resulting noncovalent arrays undergo sapphyrin-to-fullerene electron trans' er when iiradiated with 387 nm light This gives rise to charge separated states with lifetimes of ca 470 and 600 ps in the case of the 1 1 and 1 2 sapphyrin-fullerene ensembles, respectively