Preheat the oven to 350°F. Prepare the devil's food cake mix according to package directions. Place the silicone cauldron molds on a sheet pan. Divide the batter evenly between the 8 molds, filling each about two-thirds full. Bake for approximately 20 minutes, or until a toothpick inserted into the center comes out clean.
Remove from the oven and allow the cakes to cool completely on a wire rack before decorating.
While the cakes cool, make the buttercream. Beat the softened butter on medium speed until smooth and creamy, about 2 minutes. Add 4½ cups confectioners' sugar, heavy cream, and vanilla extract. Beat on low for 30 seconds to combine, then increase to medium-high and beat for 2 full minutes until light and fluffy. Add a pinch of salt and mix briefly.
Divide the buttercream between two bowls — about three-quarters into one bowl and one-quarter into the other. Tint the larger portion red and the smaller portion yellow using gel food coloring. Transfer each color into a piping bag fitted with a star tip.
Once the cakes are fully cooled, use a small sharp knife to cut a 1" divot out of the center of each cake. Spoon 2 tablespoons of chocolate syrup into each cavity. Trim the divot piece flat and press it back into the reservoir over the syrup to seal it in.
Pipe the red buttercream over the surface of each cake in spiky or swirly designs, covering the top completely. Add yellow buttercream accents. Use a toothpick to swirl the two colors together until the frosting looks like a bubbling potion.