Preheat the oven to 350 degrees.
Pulse the unsweetened chocolate with the metal blade of a food processor 4 times, then process until finely chopped, about 1 minute. With the motor running pour the hot butter through the feed tube in a slow, steady stream and process until the chocolate is melted, about 30 seconds. Scrape down the work bowl.
Add the eggs, sugar, marmalade, and vanilla and process until combined, about 5 seconds. Add the flour, baking powder, salt and semisweet chocolate and pulse until combined, about 5 times.
Pour into a greased 8-inch square baking pan and bake in the preheated oven until a cake tester comes out clean, about 30 minutes. (watch carefully). Cool on rack.
While the brownies cook, make the glaze. Pulse the chocolate with the metal blade 4 times, then process until chopped finely, about 1 minute. Combine the butter, milk, and sugar in a small saucepan and bring to a simmer, about 4 minutes. Stir in the vanilla. With the motor running pour through the feed tube in a slow, steady stream and process until the chocolate is melted, about 30 seconds.
Spread the brownies with the chocolate glaze and refrigerate until set, about 30 minutes. Sprinkle with the orange zest, cut into 2-inch squares, and halve the squares diagonally.