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Combine molasses, bourbon (or apple juice) and mustard in a small bowl. Season pork chops with 1/2 teaspoon each salt and pepper, then brush with half the molasses glaze.
Position rack in upper third of oven; preheat broiler to high.
Heat 1 tablespoon oil in a large cast-iron or other broiler-safe skillet over medium-high heat. Add the pork chops and cook until golden brown, 2 to 3 minutes per side. Transfer to a plate.
Add the remaining 1 tablespoon oil to the pan. Add bell pepper, onion and garlic; cook, stirring occasionally, until the vegetables start to soften, about 4 minutes. Add black-eyed peas, paprika, thyme and the remaining 1/4 teaspoon each salt and pepper. Cook for 2 minutes. Place the pork chops on top of the peas and pour in any accumulated juice. Brush the chops with the remaining glaze. Place the pan under the broiler. Broil until an instant-read thermometer inserted into a chop registers 145°F, 2 to 5 minutes.