Discord needs something to keep himself occupied that won't make him end up as a glorified lawn gnome for another thousand years. Knowing that causing chaos on any scale he would like is off-limits, he decides to play his hands/claws at a diversion Celestia seems to have a addiction to: teaching students!
While the search for little ponies he can tutor in the ways of chaos is cold at first, he eventually stumbles on a little pony who seems after his own twisted patchwork heart. A little pony who's bossy. A little pony who's annoying. A little pony who, just possibly, reminds him a little of himself when he was just a few thousand years old.
Indeed, this "Diamond Tiara" is going to be the best student he's ever had!