Heat oven to 350°F. Grease and line two 8-inch round pans with parchment.
Whisk flour, sugar, cocoa, baking powder, baking soda, and salt in a large bowl.
Whisk eggs, buttermilk, oil, and vanilla in a separate bowl until smooth.
Pour wet mixture into dry. Stir until mostly combined and a few streaks remain.
Stream in hot coffee. Mix until the batter looks glossy and pourable.
Divide batter between pans. Tap pans lightly to release air bubbles.
Bake 32 to 36 minutes, until a pick comes out with moist crumbs.
Cool cakes 10 minutes in pans. Turn out to racks and cool completely.
Melt chopped chocolate gently, then let it cool to lukewarm.
Beat butter until creamy. Mix in cocoa and salt until uniform.
Add powdered sugar alternately with cream. Beat until fluffy and smooth.
Blend in vanilla and melted chocolate. Adjust cream for a spreadable frosting.
Level cakes if needed. Frost between layers, then cover top and sides generously.