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In a 3 1/2- or 4-quart slow cooker combine chocolate chips, sugar, evaporated milk, butter, coffee powder, salt, cinnamon and, if desired, cayenne pepper.
Cover and cook on Low for 3 hours, stirring once halfway through cooking. Whisk until smooth. Stir in liqueur. Cool slightly.
Ladle sauce into sterilized half-pint canning jars. Seal and label. Store in the refrigerator for up to 2 weeks.