I'll start off by saying that Florence is probably my least favorite city in Europe. If you removed the tourists, it may be the best, but you can't. I'd suggest as foodguy says -- a stop. Try to take the train out, it is one of the great stations in the world. Other than that, I haven't been to any of these areas, but I have been to other remote areas in Italy and each has exceeded my expectations to a great degree. They would all be great places to spend your first weeks as a married couple.