Heat a large cast-iron skillet over high heat. Pat scallops dry with paper towels; sprinkle with salt and pepper. Lightly coat pan with cooking spray. Add scallops to pan; cook 2 minutes on each side or until golden brown. Remove scallops from pan; keep warm. Reduce heat to medium. Add rind and next 4 ingredients (through garlic) to pan; bring to a simmer. Add tomatoes; cook 45 seconds, tossing to coat.
Spoon about 2 teaspoons pesto on each of 4 plates. Arrange one-quarter of scallops and about 1/2 cup tomato mixture on each plate. Sprinkle with basil.
For a golden-brown crust on the scallops, don't disturb them while they cook except to turn them over.