I think they could. I dunno about your rainbow darters, but they don't get very big around here as adults. 1.5-2" on average, 3 inches is a substantial fish. I have a bunch of them in my 90g, and they're tiny guys, albeit adults, because the males were colored up for spawning when I caught them. One of my 2+ inch shadow bass just ate one yesterday. Took him forever to get it down but he did it.
Even if the darter seems too big to eat they might try. I catch dollars on small lures and minnows that are far too big for them to swallow. When I had them they'd go after minnows meant for my largemouth that were too big for them. They just tear them up and eat pieces if they can't get them down. If you have several dollars, or most other sunfish for that matter, if one gets a hold of something too big the others will try to get it and they'll end up tearing it to pieces and sharing it. If they get into a feeding frenzy they'll essentially try eat anything any of the others have.
Several sunfish together is actually a common tactic to get the to eat. If a few eat something the others usually will. So your problem is if even one decides darters are food the others likely will.
Now, like I said, I catch them for free, and they eat each other in the wild, so I don't mind if some fish eat others. But I'd certainly be more cautious if I paid for them and had to have them shipped.