They rely on the plane being lighter from fuel burn and therefore more efficient to extend their possible flight time, but not for safety.
Needing to land before getting under weight usually means a crash landing. In modern times, very few things like fire or an engine self-destructing will require immediately getting out of the air. It is usually better to fly in a straight line, figure out what is going on, figure out where to land, then land. This lets you get underweight, lets you communicate with air traffic control, lets emergency services prepare, etc.
Airliners will dump fuel or keep flying to get below maximum landing weight if possible. If they're still overweight and manage to land without issue, the plane will need to be inspected and repaired before it can fly again.
Contained vapor creates an explosion, while liquid must evaporate first.