In a 1-cup liquid measuring cup, combine coffee liqueur, Irish cream liqueur, and chocolate syrup.
For each serving, coarsely crumble 1/2 of a brownie into a chilled 8-ounce dessert dish or glass. Top with 1 scoop coffee ice cream; gently spreading to make an even layer. Coarsely crumble another brownie half on top of the ice cream and top with a scoop of vanilla ice cream. Place in freezer. Repeat with remaining 5 dishes.
Pour 2 tablespoons of the liqueur mixture into each glass. If desired, cover and freeze until ready to serve, or serve immediately. Drizzle with caramel topping and garnish with mint.