Whisk the coffee liqueur, water, espresso powder, and 2 tablespoons of the confectioners' sugar in a glass measuring cup until smooth. Pour about 1/3 cup of the mixture over the ladyfingers in a shallow bowl, then toss and set aside.
Gently beat with a handheld mixer the remaining espresso mixture and the remaining 4 tablespoons confectioners' sugar into the mascarpone until smooth. Take care not to overbeat it or the mascarpone will be grainy. Using the same beaters (no need to clean them), beat the whipped cream to soft peaks and fold it into the mascarpone mixture.
To assemble the tiramisu: Crumble half the soaked ladyfingers into four 8-ounce parfait or wine glasses. Spoon 1/4 cup of the mascarpone mixture over the ladyfingers and press and spread gently with the back of the spoon to fill the spaces between the ladyfinger pieces. Repeat with remaining ladyfingers and mascarpone mixture. Sprinkle 1/2 teaspoon ground chocolate over each tiramisu, cover with plastic wrap, and refrigerate for at least 1 hour or overnight before serving.
Ladyfingers are little oblong sponge cakes that look like wide fingers. We prefer the crisp Italian savoyardi variety to the soft sponge-cake type.
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