Building efficient triplet-harvesting layers for photovoltaic applications requires a deep understanding of the microscopic properties of the components involved and their dynamics. Singlet fission is a particularly appealing mechanism as it generates two excitons from a single photon. However, the pathways of the coupled triplets into free species, and their dependence on the intermolecular geometry, has not been fully explored. In this work, we produce highly ordered dilute pentacene films with distinct parallel and herringbone dimers and aggregates. Using electron paramagnetic resonance spectroscopy, we provide compelling evidence for the formation of distinct quintet excitons in ambient conditions, with intrinsically distinctive electronic and kinetic properties. We find that the ability of quintets to separate into free triplets is promoted in the parallel dimers and this provides molecular design rules to control the triplets, favouring either enhanced photovoltaic efficiency (parallel) or strongly bound pairs that could be exploited for logic applications (herringbone).