Artificial photosynthetic systems for solar energy conversion exploit both covalent and supramolecular chemistry to produce favorable arrangements of light-harvesting and redox-active chromophores in space. An understanding of the interplay between key processes for photosynthesis, namely light-harvesting, energy transfer, and photoinduced charge separation and the design of novel, self-assembling components capable of these processes are imperative for the realization of multifunctional integrated systems. We report our investigations on the potential of extended tetracationic cyclophane/perylene diimide systems as components for artificial photosynthetic applications. We show how the selection of appropriate heterocycles, as extending units, allows for tuning of the electron accumulation and photophysical properties of the extended tetracationic cyclophanes. Spectroscopic techniques confirm energy transfer between the extended tetracationic cyclophanes and perylene diimide is ultrafast and quantitative, while the heterocycle specifically influences the energy transfer related parameters and the acceptor excited state.