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To prepare cake: Butter the inside of a 2-quart slow cooker using 1 tablespoon butter; set aside. In a medium bowl, whisk together flour, pumpkin pie spice, baking powder, baking soda and salt; set aside. Whisk together the remaining 1/2 cup butter and boiling water in a large bowl, until butter melts. Add sugar, molasses, egg and zest to the butter mixture and whisk until combined. Add the flour mixture and whisk until smooth.
Spoon batter into prepared slow cooker. Cover and cook on High for 2 1/2 hours (a skewer inserted in the cake comes out with just a few moist crumbs).