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Heat broiler. Spread out tomatoes, shallots, garlic, and chiles on a rimmed baking sheet; broil, turning halfway through, until tomatoes are charred and beginning to burst, about 10 minutes. Let cool slightly.
Meanwhile, heat a large cast-iron skillet over high. Season pork chops generously with salt and pepper; rub with oil. Cook pork until browned, about 2 minutes per side. Transfer to a platter.
Transfer charred vegetables to a food processor; pulse to a coarse paste (you want some texture). Transfer sauce to a bowl and stir in lime juice, cilantro, fish sauce, and sugar. Taste and season with more fish sauce if needed.
Serve pork chops with rice and sauce for dipping.