I am reading right now The Snow Queen by Joan D. Vinge, which no one seemed to have mentioned. It's beautifully written and it won awards on top of awards. Unfortunately DTB only.
Otherwise I second those who voted for The Left Hand of Darkness by Ursula K. Le Guin, though once again DTB only. Pretty much anything by Lois McMaster Bujold would appeal to women (and some of her books are free from Baen too).
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