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Photocatalysts based on metal-organic frameworks (MOFs) are very promising due to a combination of high tuneability and convenient porous structure. Introducing porphyrin units within MOFs is a potential route to engineer these natural photosynthesis molecular catalysts into artificial photosynthesis heterogeneous catalysts. Using computer simulations based on density functional theory, we explore how to modify the electronic structure of porphyrin-based MOFs to make them suitable for the photocatalysis of solar fuel synthesis via water splitting or carbon dioxide reduction. In particular, we have investigated the effect that Fe substitutions have on the electronic properties of porphyrin-based metal organic frameworks. By aligning the electron levels with a vacuum reference, we show that Fe at the porphyrin metal centre has the effect of slightly raising the position of the valence band edge, whereas Fe at the …