Well i'm not sure if its the first time we have blatantly seen the imperius curse used - apart from perhaps the fake moody in #4? in DADA class, but i was amazed when harry did as they entered gringotts!
Griphook warned him that the goblins were aware they were intruders..

Harry raised the hawthorn wand beneath the cloak, pointed it at th goblin and whispered, for the first time in his life, 'Imperio!'

also i dont think we've seen anyone confunded before, harry had to confund the security at gringotts in order for them to think they had already checked them for magically concealed objects

also the protection charms used by hermione to secure their position..
and used in lovegood's house to blast a hole in the floor (Deprimo)
actually most of the new ones were hermiones
- wiping memories
- changing appearances