Chop chocolate and combine with hot coffee in bowl. Stir until chocolate is melted and smooth. Sift all dry ingredients in a large bowl. In a mixer, beat eggs until thickened (about 2 minutes). Slowly add oil, buttermilk, vanilla and melted chocolate mixture to eggs to combine. Add sifted dry ingredients and beat on medium speed until well combined. Place in large cupcake papers, and bake at 350 for 10 minutes.
Melt the chocolate and cool to room temperature. In a mixer, with a paddle, process butter, sugar, cocoa, salt, cinnamon, ancho chili powder and cayenne until smooth. Add corn syrup and vanilla and process until smooth.Add chocolate and pulse until creamy and smooth, about 10 seconds.