We investigate the dynamics of intramolecular singlet fission in a dimer consisting of two pentacene-based chromophores covalently bonded to a phenylene spacer using an approach that combines high-level ab initio multireference perturbation theory methods and quantum dynamical simulations. The results show that the population of the multiexcitonic state, corresponding to the first step of singlet fission, is facilitated by the existence of higher-lying doubly excited and charge transfer states that participate in a superexchange-like way. The important role played by high-frequency ring-breathing molecular vibrations in the process is also discussed.