Round 4 they may declare war on any/all axis at the beginning of their collect income phase. They are not required, but definitely should do so unless looking for the fabled isolationist victory.
To get this straight, though. If directly attacked, the US is at war on the attacking powers turn. The industrial complexes get upgraded immediately and can be used on the US next turn
If an ally is attacked in a way that allows the US to come into the war. The US must still declare war on her turn at the beginning of the conduct combat phase.
This is where it becomes ambiguous. The US did not purchase the industrial complex to be deployed during the Mobilization phase as would normally be the case. She didn’t have the major complex at the beginning of her turn (though she did possess the minor complex), but there is no restriction saying that you must purchase only the number of units you are able to place.
So the question is does the US meet the requirements to utilize the major complex, which are
1 Must not have captured or purchased the IC this turn
2 You can use an industrial complex that you controlled at the beginning of your turn
The US meets 1 clearly, but strictly speaking does not meet 2 (did not contrll the major complex at the beginning of the turn so can’t use it)
From Larry’s Site Rule Clarifications:
Mobilizing New Units
When upgrading a minor industrial complex to a major one, only three units may be mobilized by the complex in the same turn (not counting the upgrade itself).