What should Mr. Platonic (Really) do?
You're being a good friend, not a lover, so yes, you're totally over-thinking this. Her husband's feelings are her responsibility -- ask her if he's fine with it, then let it go.
She has a new baby and can't make friends? I don't buy that. Every town in this country is overrun with mom-and-baby groups. Encourage her to join some -- then babysit so she can have a ladies' night.
Strictly platonic? There's no such thing for exes. There's a reason you feel uncomfortable with this friendship. Back off a little so she's forced to make new friends.
That's a new low. If YOU'D be worried or angry, why would you do this to someone else who's risking his life to protect your freedom?
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