In a medium bowl, sift the flour, baking powder, baking soda, salt, and cocoa powder. Set aside.
Stir the hot coffee, semi-sweet chocolate, and espresso powder together in a small bowl. Microwave in 15-second intervals until the chocolate is melted and smooth.
In a large bowl, whisk the vegetable oil, granulated sugar, and room temperature eggs until smooth. Add the coffee mixture, whole milk, and whisk until smooth. Add the dry ingredients and whisk until the batter is smooth.
Pour the batter into the cupcake liners and bake the cupcakes for 16-17 minutes. A toothpick inserted into the center should come out clean. Allow the cupcakes to cool in the pan, then remove from the pan and cool completely on a plate or wire rack before frosting.