We have constructed supramolecular solar cells composed of a series of porphyrin-peptide oligomers [porphyrin functionalized a-polypeptides, P(H 2 P) n or P(ZnP) n (n = 1, 2, 4, 8, 16)], and fullerenes assembled on a nanostructured SnO 2 electrode using an electrophoretic deposition method. Remarkable enhancement in the photoelectrochemical performance as well as the broader photoresponse in the visible and near-infrared regions is seen with increasing the number of porphyrin units in a-polypeptide structures. Formation of supramolecular clusters of porphyrins and fullerenes prepared in acetonitrile-toluene = 3 : 1 has been confirmed by transmission electron micrographs (TEM) and the absorption spectra. The highly colored composite clusters of porphyrin-peptide oligomers and fullerenes have been assembled as threedimensional arrays onto nanostructured SnO 2 films using an electrophoretic deposition method. A high power conversion efficiency (g) of y1.6% and the maximum incident photon-tophotocurrent efficiency (IPCE = 56%) were attained using composite clusters of free base and zinc porphyrin-peptide hexadecamers [P(H 2 P) 16 and P(ZnP) 16 ] with fullerenes, respectively. Femtosecond transient absorption and fluorescence measurements of porphyrin-fullerene composite films confirm improved electron-transfer properties with increasing number of porphyrins in a polypeptide unit. The formation of molecular assemblies between porphyrins and fullerenes with a polypeptide structure controls the electron-transfer efficiency in the supramolecular complexes, meeting the criteria required for efficient light energy conversion.

Organic photovoltaic cells using supramolecular complexes of porphyrin-peptide oligomers (porphyrin-functionalized alpha-polypeptides) with fullerene demonstrate remarkable enhancement in the photoelectrochemical performance as well as broader photoresponse in the visible and near-infrared regions by increasing the number of porphyrin units in alpha-polypeptide structures. A high power conversion efficiency (eta) of 1.3% and a maximum incident photon-to-photocurrent efficiency (IPCE) of 42% were attained using composite clusters of porphyrin-peptide octamer and fullerene. These results clearly show that the formation of a molecular assembly between fullerene and multi-porphyrin arrays with a polypeptide backbone controls the electron transfer efficiency in the supramolecular complex, which is essential for the light-energy conversion.