Gems cannot buy you saints, directly. Indirectly, yes. You can use gems to buy a card from the fair, or to buy credits to use the tavern.
The checkbox in the hero sanctify tab for 100 gems is simply a safeguard to protect you if the card fails. Spend 100 gems and if it fails, you retain the card to try again, and so on.
Leader cards are a bit tougher to get your hands on.





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