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Preheat the oven to 350, and line 4 cups with cupcake liners in a muffin pan.
In a small bowl, whisk together the flour, cocoa powder, baking soda, and baking powder.
In a medium bowl, whisk together the espresso powder (if using), oil, vanilla and brown sugar.
Add half of the dry ingredients to the oil mixture, and mix well.
Then, add half of the buttermilk and continue to stir.
Finally, add the remaining flour followed by the buttermilk, and stir everything until evenly combined.
Divide the batter between the prepared muffin cups.
Bake for 16-17 minutes, until the tops spring back and a toothpick inserted in the center comes out clean with only moist crumbs clinging to it.
Let the cupcakes cool completely.
In a small bowl, beat together the marshmallow fluff and butter until light and fluffy.
Scrape the marshmallow mixture into a piping bag (or plastic bag with the tip cut off), and insert a large frosting tip.
Pipe the marshmallow filling into the center of each cupcake. (See photo for reference).
Watch the surface of the cupcakes carefully as you pipe the marshmallow filling inside--it will slightly puff up when it's at capacity.
Next, melt the chocolate and coconut oil in 30-second pulses in the microwave. Dunk each cupcake upside down in the melted chocolate, and let set before serving.