The behavior of A3C60 superconductors at the large inter-fulleride separation where the transition temperatures (Tc) are highest is investigated by the synthesis and structural and electronic characterization of face-centered cubic (fcc) A3C60 compounds with the largest lattice parameters yet found. In this family Tc decreases with increasing inter-fulleride separation, despite a continued increase in the density of states at the Fermi level. This contrasts with Tc(a) relationships previously demonstrated for these materials and is consistent with recent suggestions that the interelectron repulsions between carriers in the t1u band are important in determining Tc in a fulleride metal near the Mott−Hubbard transition