Preheat oven to 350°F. Line muffin tins with 12 cupcake liners.
In a medium bowl, whisk together the flour, cocoa powder, baking soda, baking powder, salt, and instant espresso powder.
In a small bowl, whisk together the buttermilk, oil, sugar, egg, and 1 teaspoon vanilla until smooth and well combined.
Add the wet ingredients to the dry and stir until just combined.
Slowly whisk in the hot coffee. The batter will be thin, similar to thick hot chocolate consistency.
Fill cupcake liners about 2/3 full. Bake for 18 minutes or until a toothpick inserted in the center comes out with a few moist crumbs, and the tops bounce back after lightly pressing on them. Allow to cool to room temperature before filling and frosting.
Beat butter until light and fluffy, about 2-3 minutes. Add the powdered sugar and beat on low speed until incorporated, then increase the speed to medium and beat until mixed well. Beat in the marshmallow fluff until fully incorporated. Add the heavy cream, vanilla, and salt. Beat on medium-high for 2-3 minutes until fluffy. Chill until ready to use.
Place the semi-sweet chocolate in a small bowl and pour the warmed heavy cream over top. Let sit undisturbed for 2 minutes, then stir until glossy and smooth. Allow the ganache to set for about 20 minutes.
Transfer the marshmallow cream filling in a piping bag fitted with a tip that will easily fill the cupcake centers.
Cut a small cone out of the center of each cupcake with a sharp knife. Remove the top portion of the cupcake cone and set it aside. Scrape any cupcake crumbs from the knife onto the rim of a bowl between cuts. Fill the cavity with 1-2 teaspoons of marshmallow cream, then replace the cupcake top.
Spread the chocolate ganache over each cupcake and allow it to set for about 20 minutes.
Pipe a thin squiggly line over the top of the ganache to create that classic Hostess-inspired cupcake design.
Serve immediately and enjoy!