Preheat oven to 350 degrees. Grease a 15x10x1-inch cookie sheet.
In a saucepan, combine your water, 1 cup butter, and 1/3 cup of cocoa powder. Turn heat to medium and melt the butter, stirring periodically. Bring to a boil, stirring constantly as it starts to warm. Remove from heat once it boils.
1 cup water, 1 cup unsalted butter, 1/3 cup cocoa powder
In a medium bowl, add flour, sugar, baking soda, cinnamon, chili powder, and salt, then stir. Add melted butter and cocoa mixture to dry ingredients and mix on medium speed until incorporated. Add eggs, 1/2 cup buttermilk, and vanilla, and beat for a minute.
Pour into prepared pan and bake at 350 degrees for 30-35 minutes, until cake tester comes out clean.
Make frosting near the end of the baking time. In a saucepan, combine remaining 3 tablespoons butter, 5 tablespoons cocoa powder, and 1/3 cup buttermilk and turn the stove to medium. Bring mixture to a boil, then remove from heat.
Add powdered sugar and the last 2 1/2 tablespoons vanilla and mix, starting on low until the powdered sugar is incorporated, then beating on high until the mixture is smooth.
Pour still warm frosting over brownies. Gently spread icing from the center to edges. Let the brownies cool at least 2 hours, then cut into pieces.
Notes
Store any leftovers in a tightly sealed container on your counter for 2-3 days. These also freeze extremely well for 1-2 months (and are tasty straight from the freezer).
For more tips and tricks, be sure to read the full article above.