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If it is not your turn, and you are considering using this Class die (once per round) on another player's turn, can you wait to see what the monster roll is as well as what the other player's combat roll is before making the decision as to whether it is worthwhile to roll the Assassin die?
Yes, I think the timing is fairly open. If you're going to have impact however you'll need to do it while the combat is in progress and before resolution since your abilities directly affect combat values.