Start heating a large, nonstick frying pan over medium-high heat. Coat the outside of the chicken breasts with olive oil and add to the hot frying pan. Sprinkle seasoning over the chicken. When the bottom is nicely brown, about 2 minutes. Flip chicken breasts over to brown other side, about 2 minutes.
Add lightly cooked potato pieces to bottom of slow cooker. Pour in low-sodium chicken broth. Spread pesto evenly over the top, and sprinkle chopped red pepper over the top. Gently toss mixture. Lay browned chicken breasts over the top of the potato mixture. Cover and cook on high for about 3 hours or low for about 6 hours.