The short answer is that nothing magical happens in AOW, that makes it safe for you to go to 100 feet. But in theory, you have at least five more dives under your belt, and have had a chance to see what narcosis feels like and how much it affects you at that depth, and you've had a chance to talk a bit more about how fast your gas disappears on deeper dives. You've done a little more navigating, and perhaps a dive in the dark (since it's often dark at those depths).
Sadly, those five dives and the learning that comes with them are often not enough to make it safe for divers to go to those depths. I've read too many reports (and know of at least one local case) where someone just out of AOW does a deep dive and runs out of gas. An AOW cert does not relieve the diver of the need to pay close attention to his pressure gauge, and since the class is often taught shortly after OW, the graduates are often still new enough to have VERY high gas consumption rates. Deep dives, high consumption, and often small tanks are a recipe for urgent ascents and OOA scenarios.