Dark Star/ Fallen Star Guardian Syndra
When I read Star Guardian Janna's related lore, I noticed how Riot put their collective foot in the door for adding further star guardian skins, or at the very least some extra lore regarding the star guardians (such as what killed 4 guardians, and left Janna a sole survivor).
Now my idea, as evidenced by the title, is a skin for Syndra to show what happened to at least one of the lost 4, possibly all 4. Syndra could have been the first squad's powerhouse, wanting to push her abilities past her limits constantly. Eventually she hits a wall, and no matter how hard she tried, she couldn't push herself past this limit.
Now this is where the "fallen guardian" vibe comes in. In order to get past this barrier, Syndra may have dipped into the power of the Dark Star, to get even more power. A possibility could be that in order to gain access to the Dark Star, she had to betray the other guardians, and Janna was the only guardian to have survived/escaped what ever trap the forces of the Dark Star had set up with Syndra's inside help.
Another possibility (one that doesn't make Syndra look like a complete villian) is that the guardians were defeated, with Janna being the only one who escaped this defeat, and Syndra had been captured, rather than killed like the others, and subsequently turned into a minion of the Dark Star.
My third and last idea, is that in Syndra's pursuit of ever greater power, she eventually challenged the source of the power of the star guardians(the first light I think is what it's called), wanting all of it, be defeated and cast out, and have no choice but to turn to the Dark Star for more power ( this last idea sort of mirrors the fall of Lucifer, once God's favored angel, who challenged God, was defeated, and then cast out of Heaven and into Hell).
With these scenarios in mind, now for physical descriptions. To show the Dark Star's influence on Syndra, but balancing that with her origin as a Star Guardian would be rather difficult. A simple solution may be to give Syndra the regular Star Guardian garb, but have it show signs of corruption, be it slightly tattered, Dark Star color themes, or a more complicated solution, just give her a Dark Star themed costume.