I don't know the relative expansion rates for copper and pex, but they both expand when heated. As to running pex along the baseboard, two thing: will sunlight strike it (not good for extended periods), and will it be protected from potential knocks and cuts (copper will dent, but is much harder to cut)? I'd lean towards copper for the increased flow, impact resistance, and UV tolerance. Pex would be cheaper and require fewer joints.