I suppose it has something to do with the latent heat of cristalization and the low surface radius on that side of the heart-shape (lower radius means higher latent heat in the time unit). Maybe that single mold was in a hotter zone or had less air circulation or something else that prevented the latent heat to be dissipated correctly. Try to put the molds in a colder place after pouring the first chocolate layer (the outer shell).
Teo