Melt in double-boiler: chocolate, sugar, butter over simmering water. Remove bowl. Cool to room temperature. Preheat oven. Coat bottom and sides of baking pan with nonstick spray. Cut and place parchment paper and spray again. As chocolate cools, measure 1/4 cup cocoa and sift into bowl containing flour, baking powder, and salt.
Whisk ingredients together.
Beat eggs, espresso powder, and vanilla until foamy, scraping once. Beat in cooled chocolate mixture, scraping once. Sprinkle small amount of flour in chocolate mixture and fold. Repeat. Add remaining flour. Fold in until no flour appears. Spread batter evenly in pan. Bake in center of oven 22–25 minutes or until a toothpick inserted in center is barely moist. Remove from oven and cool completely. Run knife around edge of pan. Place rack on top of pan and invert. Peel paper. Invert again onto cutting surface. With a sharp knife, trim off edges and cut brownies into 2" squares.
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