It sounds like adding a gigabit switch is the right way forward, though I know you said you can't. (Which also seems really weird to me. You can get a 5-port Gigabit unmanaged switch for under $20, and it only takes up a tiny footprint.)
In the end, you could do direct links between the FreeNAS and each PC. Then, if you need to move data from one PC to the other, you could just copy it to the FreeNAS server, and then to the other PC.
However, if you want to create a network out of those two PCs and a FreeNAS, you're going to need some extra hardware or software: and I would strongly discourage you from trying to bastardize your FreeNAS system with the software necessary to make this work.
Honestly, it kinda feels like you're being cryptic about your needs here. I struggle to come up with the background to the scenario you've found yourself in, and I'm skeptical that it's the whole story (though that doesn't mean I'm always right :D). I'm genuinely curious to hear the back-story to all this, and maybe a few more details about your limitations. I think you've got a few implied solutions here, and with a little more knowledge we may be able to figure out something that works great :)