Preheat oven to 350°F. Place a rack in the center. Line a 9×13" pan with foil and spray the foil with cooking spray.
Place the 2 ounces unsweetened baking chocolate, 2 ounces semi-sweet baking chocolate, and ¾ cup unsalted butter in a large microwave-safe bowl. Microwave on HIGH for 2–3 minutes, stirring every 30 seconds, until the chocolate and butter are melted and smooth. Let the mixture sit 1–2 minutes to cool slightly.
Stir in 1¾ cups sugar until combined.
Add the 3 large eggs, one at a time, stirring after each egg until fully incorporated. Stir in 1 teaspoon vanilla extract.
Reserve the topping spices: set aside ¼ teaspoon unsweetened cocoa powder, ¼ teaspoon ground cinnamon, and 1/8 teaspoon ground cayenne pepper for the topping. To the batter, add the remaining cocoa and spices: 2 tablespoons unsweetened cocoa powder, 1 teaspoon ground cinnamon, ¾ teaspoon ground cayenne pepper, and ¼ teaspoon salt. Stir until evenly mixed.
Add 1 cup all-purpose flour and stir just until the flour is incorporated. Do not overmix.
Fold in ¾ cup mini chocolate chips.
Spread the batter evenly in the prepared 9×13" pan.
Bake 20–25 minutes, or until a toothpick inserted into the center comes out with just a few moist crumbs clinging to it. Remove from oven and let the brownies cool completely in the pan on a wire rack.
Once cooled, lift the brownies from the pan using the foil and place on a cutting board. Slice into squares. In a small bowl whisk together 1 tablespoon powdered sugar, the reserved ¼ teaspoon cocoa powder, the reserved ¼ teaspoon cinnamon, and the reserved 1/8 teaspoon cayenne pepper. Sprinkle this mixture over the sliced brownies.