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Line a large baking sheet with foil, extending excess over edges of pan. Set pan aside. Butter the sides of a heavy 3-quart saucepan. Melt 2 cups butter in saucepan. Add sugar, water, molasses and 3 teaspoons espresso powder. Cook and stir over medium-high heat until mixture boils.
Clip a candy thermometer to side of pan. Reduce heat to medium; continue boiling at a moderate steady rate, stirring frequently, until thermometer registers 290°F, soft-crack stage (about 25 minutes). Watch carefully after 280°F to prevent scorching.
Remove saucepan from heat; remove thermometer. Stir in vanilla. Pour candy into the prepared pan. Let candy stand about 1 hour or until firm. Use foil to lift candy out of pan. Break candy into pieces that are about 2 inches in size.
Melt the remaining 3 tablespoons butter in a heavy medium saucepan. Stir in the remaining 1 teaspoon espresso powder until dissolved. Add chocolate chips and melt over low heat, stirring often. Place pecans in a shallow dish or on wax paper.
Dip half of each candy piece into the melted chocolate mixture, coating all sides. Place dipped candy on wax paper. Sprinkle with pecans. Chill until chocolate is firm. Store in a tightly covered container.