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1. For a gas or charcoal grill, place peppers on the rack directly over medium heat. Cover and grill for 12 minutes, or until blackened and blistered, turning occasionally. Transfer peppers to a bowl. Cover bowl with a plate or plastic wrap. Let peppers stand 20 minutes. Discard skins, seeds, and cores, then thinly slice peppers. Set aside.
2. Using a chefs knife, mince and mash garlic with 1/4 teaspoon of the salt to make a paste. Transfer to a large bowl. For marinade, add 1/4 cup of the oil, 1 tablespoon of the vinegar, 1/2 teaspoon salt, and 1/2 teaspoon pepper to mashed garlic, whisk to combine. Halve zucchini lengthwise, then coat with marinade in bowl. Transfer zucchini to grill rack (do not wash bowl). Grill zucchini, covered, 8 to 10 minutes or until tender, turning occasionally. Transfer zucchini to a serving platter.
3. For chimichurri, in the marinade bowl stir together reserved grilled peppers, herbs, the remaining 1/2 cup olive oil, remaining 1 tablespoon vinegar, and remaining 1/4 teaspoon each salt and pepper. Spoon chimichurri over zucchini.