Preheat oven to 350°F (175°C). Grease two 9-inch round cake pans, line with parchment, grease again, and dust with cocoa powder.
Whisk flour, sugar, cocoa powder, baking powder, baking soda, and salt in a large bowl.
Add eggs, buttermilk, oil, and vanilla. Mix until smooth.
Slowly pour in hot coffee (or hot water) while mixing until batter is thin and pourable.
Divide batter between pans. Bake 26 to 32 minutes, until a toothpick comes out with moist crumbs. Cool 10 minutes in pans, then cool completely on a rack.
Beat butter and shortening until fluffy. Mix in powdered sugar, vanilla, and salt. Add marshmallow crème and beat until light. Add heavy cream 1 tablespoon at a time only if needed to reach a spreadable, stable texture.
Level cake layers if needed. Place one layer on a plate, spread filling evenly, then top with second layer.
Chill assembled cake at least 45 minutes.
Place chocolate chips in a bowl. Heat heavy cream until steaming and bubbling at the edges, then pour over chips. Rest 2 minutes, then stir until smooth. Mix in corn syrup (optional), vanilla, and salt.
Pour ganache over chilled cake and spread gently to the edges. Chill 20 to 30 minutes to set before slicing.