Nowadays both of them cant, knuckles can use the master emerald, but there are multiple answers, in the comic series knuckles can use the emeralds like in "sonic and knuckles" for the genesis, except updated like now. Now tails, tails had a super form with the backwards compatibility of "Sonic 3" and "Sonic and Knuckles" when anda got the chaos emeralds in both games, but, When the emeralds became super, when that happened Sonic and Knuckles would have a Hyper form while tails had just a super form, look it up hes actually pretty cool he was glowing yellow with Flicky's flying around him that would attack and grab items as anda moved.
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shizno is right , although tails and knuckles could use them in sonic 3 & knuckles in reent games they havnt used them , in sonic Heroes sonic uses the emeralds to make tails and knuckles superpowered , but not in there super form.
Tails Super Tails: Super Emeralds Hyper Tails: Same As Hyper Sonic Turbo Tails: Chaos Emeralds and Master Emerald Titan Tails: I got the power (True)
Knuckles Chaos Knuckles: Chaos Emeralds Hyper Knuckles: Same as Hyper Sonic Super Knuckles: Super Emeralds Enerjak: Master zamrud, emerald and Mind Control