Quark (QRK) deserves a spot on here. Multiple different hashing algos makes it stand out from a lot of others and this also makes it quite secure to mine. Definitely innovative.
Multiple hashing algorithms
Was QRK the first?
I think I heard of RU having it first.
this does not sound like it:
"RuCoin project is not intended that any develop and improve, and vice versa, is the most conservative position in order to maintain and use all that has been proven in Bitcoin."
https://bitcointalk.org/index.php?topic=48582.msg577990#msg577990