Preheat oven to 350°F. Line a 9x13" pan with foil and coat the foil with cooking spray.
Place the coarsely chopped unsweetened baking chocolate (2 ounces), coarsely chopped semi-sweet baking chocolate (2 ounces), and 3/4 cup butter in a large microwave-safe bowl.
Heat the chocolate and butter on HIGH for 2–3 minutes, stirring every 30 seconds, until the mixture is completely smooth.
Stir in 1 3/4 cups sugar until combined.
Add 3 eggs, 1 tablespoon vanilla extract, and 2 tablespoons unsweetened cocoa powder; stir until smooth and uniform.
Stir in 1 cup all-purpose flour just until no streaks of flour remain. Do not overmix.
Spread the batter evenly in the prepared pan.
Bake about 25 minutes, or until a toothpick inserted into the center comes out with a few moist crumbs but no wet batter. Remove from oven and let the brownies cool completely in the pan on a wire rack.
Meanwhile, make the frosting: place 1 cup (2 sticks) softened butter in a large bowl and beat with a hand mixer until smooth.
Gradually add 4 cups powdered sugar, beating on low speed until the mixture is crumbly and begins to thicken.
Beat in 3 tablespoons fresh-squeezed orange juice until incorporated, then beat in 1 tablespoon heavy cream until the frosting is smooth and spreadable. Stir in 1 teaspoon orange zest.
Spread the frosting evenly over the cooled brownies. Use the foil to lift the brownies from the pan for easier slicing, if desired.