Preheat oven to 175°C (350°F). Line an 8×8-inch pan with parchment paper, leaving 5 cm overhang on two sides.
Melt butter and chopped chocolate together over a double boiler, stirring until smooth and glossy. Cool for 10 minutes.
Whisk sugar into the chocolate mixture. Add eggs one at a time, whisking vigorously after each. Add vanilla. Whisk 1 minute until glossy and ribbon-like.
In a separate bowl, whisk together flour, espresso powder, and salt. Add to chocolate batter and fold with a rubber spatula just until no dry streaks remain — do not overmix.
Pour batter into prepared pan and smooth the surface. Bake on the middle rack for 22 to 25 minutes until a toothpick inserted in the centre comes out with moist crumbs. Cool to room temperature (30 min), then refrigerate 20 minutes.
Brush all 60 ml of cooled espresso evenly over the cold brownie base. Let absorb for 1 minute.
In a cold mixing bowl, beat mascarpone, heavy cream, powdered sugar, and vanilla on medium-high for 60 to 90 seconds until soft, billowy peaks form. Stop at soft peaks — do not overwhip.
Spread mascarpone mixture evenly over the espresso-soaked base. Sift cocoa powder in an even layer over the surface. Cover and refrigerate for a minimum of 2 hours.
To slice: lift bars from pan using the parchment overhang. Run a sharp knife under hot water, wipe dry, and cut into 16 squares — wiping and re-warming the knife between every cut.