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1. Lightly coat the inside of a 3 1/2- or 4-quart slow cooker with cooking spray; set aside.
2. In a medium saucepan, heat milk over medium heat until very warm but not boiling. Remove from heat. Add chocolate pieces and the 3/4 cup cocoa powder (do not stir); let stand for 5 minutes. Whisk until smooth; cool slightly (about 10 minutes).
3. In a large bowl, whisk together the eggs and chocolate mixture. Gently stir in bread cubes. Transfer bread mixture to the prepared cooker.
4. Cover and cook on low-heat setting (do not use high-heat setting) for about 2 1/2 hours or until a knife inserted near center comes out clean (mixture will puff).
5. Remove liner from cooker, if possible, or turn off cooker. Let pudding stand, uncovered, for 30 minutes to cool slightly before serving (pudding will fall as it cools).
6. To serve, spoon warm pudding into dessert dishes. If desired, top each serving with whipped cream and sprinkle with additional presweetened cocoa powder.