Spray the inside of a 6 quart slow cooker with cooking spray. Arrange the chopped vegetables on the bottom of the slow cooker.
Arrange the chicken and pineapple chunks on top.
In a medium bowl whisk together pineapple juice, ketchup, rice wine vinegar, granulated sugar, soy sauce, tomato paste, honey or brown sugar, garlic, Chinese 5-Spice powder, ginger, red pepper flakes, salt and black pepper. Pour on top of the chicken and pineapple.
Cook on low for 5 hours or until the chicken is fork tender and cooked through. Increase the slow cooker to the high setting.
Dissolve the cornstarch in cold water. Whisk into the sauce until thickened.
Simmer on high for 10-15 additional minutes. Serve over rice.
Notes
To add Vegetables at the end of Cooking: Omit the vegetables at the beginning of preparation. a) Cook the chicken and pineapple in the slow cooker with the sauce as directed. Add the vegetables during the last 1 hour of cooking. Thicken the sauce with cornstarch and water per the recipe, before serving. b) Alternatively, stir-fry the bell peppers and onion in a couple of drizzles of oil in a skillet on the stove-top. Season with salt & black pepper to your taste. Thicken the sauce in the slow cooker per the recipe, then stir in crisp-cooked vegetables just before serving.Chinese 5-Spice powder includes; cinnamon, fennel, schezwan peppers, star anise and clove ground into a spice blend. It's readily available on the spice aisle or in the Asian section of most grocery stores.