摘要： Chromophore aggregation strongly impacts the efficiency of organic photovoltaics (OPVs). Perylene-3,4:9,10-bis(dicarboximide) (PDI)-based electron acceptors have been shown to be excellent alternatives to fullerenes in OPVs, provided their supramolecular assemblies do not form excimers. In order to study this phenomenon in a controlled fashion, we have prepared two PDI derivatives that were incorporated into an anodic aluminum oxide (AAO) membrane. In one system, the PDI molecule has an n-propyl silatrane attached to one of its imide nitrogens, while a 12-tricosanyl group is attached to the other imide nitrogen. The silatrane reacts with the AAO surface to covalently bind the PDI. The other PDI has 12-tricosanyl groups on both imide nitrogens, which intercalate with n-octadecylsilane chains covalently bound to an AAO membrane. Since aluminum oxide is a wide bandgap semiconductor, photoexcitation of PDI does not result in charge injection into the AAO membrane; thus, the intrinsic electronic properties of the aggregated PDI molecules within the membrane can be studied. Both PDI derivatives form excimers upon photoexcitation with and without solvent in the AAO membrane pores which display increasing charge transfer character with increasing solvent polarity. Since the AAO membrane allows for any choice of solvent to be infiltrated into its pores, the PDI photophysics can be modulated over an arbitrary range of solvent polarities, irrespective of whether PDI is soluble in a particular solvent. The results presented here show how to tune the intermolecular interactions of PDI and related rylene dyes attached to walls of the AAO pores to understand the intermediate regime between solution and the solid state.