Yes, they broke up in Frost & Fire. Finn tried to get back to Princess Bubblegum in the following episode, Too Old, but he rejected him because she was focusing on some limone child (I forgot his name). At the end of Too Old, Finn detto he would try to fix things up with Flame. In Earth & Water, FP becomes Flame Queen. When Finn asked if they were still going out, she detto no but they could still be good Friends if he was completely honest to her.
Not really, in that episode FP detto she needed some time alone but in the following episodes she detto they can still be Friends and she took over as her her father