Preheat your oven to 350°F. Line a 12-count muffin pan with cupcake liners and lightly spray the inside of each with non-stick cooking spray.
In a medium bowl, whisk the flour, baking powder, baking soda, and salt, and set aside.
In a large bowl, use a hand-held mixer or use the paddle attachment in a stand mixer to mix the softened butter and sugar until combined and light and fluffy. Scrape the sides of the bowl with a rubber spatula a couple of times or as needed. Add the room temperature eggs, one at a time, and mix until just combined after each.
Add the vanilla extract, full-fat sour cream, and Bailey's cream liqueur. In a separate bowl, use a whisk to mix the hot coffee, cocoa powder, and instant espresso powder until dissolved. Add that to the bowl of the wet ingredients and mix until smooth. Use a rubber spatula to scrape the sides of the bowl. Add the dry ingredients and mix until smooth with no lumps in the batter.
Add the batter evenly to the cupcake liners, filling each about ¾ of the way full. Gently tap the pan on the counter to get rid of any trapped air bubbles in the batter.
Bake in the preheated oven for 15-17 minutes. A toothpick inserted in the center should come out clean. Remove from the oven and let cool in the pan, then remove from the pan and let cool completely in the fridge before frosting the cupcakes.
Make the frosting: In a large bowl, use a hand-held mixer to mix the softened butter, powdered sugar, Bailey's cream liqueur, espresso powder, cocoa powder, and salt. Mix until smooth. Add the frosting to a piping bag and decorate the cupcakes as desired. I used a Wilton 1M tip, which is a large open star tip.