PREHEAT oven to 350º F. Grease 6 jumbo muffin cups*.
MICROWAVE chocolate in small, uncovered, microwave-safe bowl on MEDIUM-HIGH (70%) power for 45 seconds; STIR. If pieces retain some of their original shape, microwave at additional 10- to 15-second intervals, stirring just until melted. Cool to room temperature.
DISSOLVE instant coffee in hot water in small bowl. Combine flour, baking soda and salt in small bowl. Beat brown sugar, oil and eggs in large mixer bowl for 2 minutes. Beat in melted chocolate and vanilla extract. Beat flour mixture into creamed mixture alternately with buttermilk. Beat in coffee mixture. Spoon into prepared muffin cups, filling 2/3 full.
BAKE for 18 to 23 minutes or until wooden pick inserted in centers comes out clean. Remove to wire rack and cool for 10 minutes. Remove from pan and cool completely.
*NOTE: To bake in standard muffin pan, spoon batter into greased muffin cups, filling 3/4 full, and bake for 18 to 23 minutes. Makes 12 muffins.
PLACE chocolate in small bowl.
MICROWAVE cream in small, uncovered, microwave-safe bowl on HIGH (100%) power until boiling. Pour over chocolate and stir until smooth. Stir in liqueur until smooth. Cool for 10 minutes; pour over cupcakes. Makes 1 cup.
INVERT cupcakes onto plates. Brush or spoon liqueur over tops. Pour ganache over each cupcake. Serve immediately.