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Habanero-Marinated Pork Chops With Mustard Greens Slaw

['2 lemongrass stalks, tough outer layers removed', '1 habanero chile, seeded, very finely chopped', '2 garlic cloves, crushed', '1/2 cup fresh orange juice', '2 tablespoons fish sauce (such as nam pla or nuoc nam)', '2 tablespoons light brown sugar', '6 tablespoons unseasoned rice vinegar, divided', '4 (1/2"-thick) bone-in pork chops', '3 tablespoons olive oil, plus more for grill', 'Kosher salt, freshly ground pepper', '1 jicama, peeled, sliced 1/4" thick', '1 bunch mustard greens, thick stems removed, sliced (about 8 cups)', '1/2 cup torn basil leaves']

Using the back of a chef's knife, lightly smash lemongrass, then thinly slice. Combine lemongrass, chile, garlic, orange juice, fish sauce, brown sugar, and 4 tablespoons vinegar in a small bowl. Pour half of marinade into a large resealable plastic bag; reserve remaining marinade.
Prick pork chops all over with a fork and add to bag; seal and turn to coat. Let marinate at room temperature, turning occasionally, at least 30 minutes.
Prepare grill for medium-high heat; oil grate. Remove pork chops from marinade and pat dry. Season with salt and pepper. Grill, turning occasionally, until charred and cooked through, 6–8 minutes. Transfer to a platter and let rest 5 minutes.
Meanwhile, season jicama with salt and grill until lightly charred, about 3 minutes per side. Cut into bite-size pieces and toss in a large bowl with mustard greens, basil, and remaining 3 tablespoons oil and 2 tablespoons vinegar; season with salt and pepper.
Taste reserved marinade and season with salt, if needed. Serve pork chops with slaw alongside and marinade for drizzling over.
Pork chops can be marinated 2 hours ahead. Chill.

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