Yes - but my main concern would be how difficult it would be to build the caves. In a tank that size, I've found that it'd best have about 20+ fish, though I wouldn't put more than 25. Yes, yes, I know.. it'd be overstocked according to the typical stocking rules (1" of fish per gallon) but that's the best way to setup an African Cichlid community tank.
You will need to have at least 2 caves per fish - and if you get much less than 20 fish, you'll see some die-off due to their aggression. With 20+ fish, though, the aggression is well dispersed. They sell rock called "lace rock" at the pet stores around me, and it comes in a huge variety of shapes and is the best I've found for making caves. It also buffers the water by leaking out minerals - the lakes these Cichlids typically live in have a high pH, usually between 8.0 and 8.4, depending on the lake/location. You'll need to either pick a side of the tank to lean the rocks on or use aquarium safe silicone to stick them in place. I'm afraid a hex is probably the hardest tank to aquascape for rock caves.
Depending on the petshops nearby, you may be able to find a very large variety of Cichlids in stock. I'm lucky enough to have a store that stocks with almost half Cichlids, but you'll be able to find Venestus, Yellow Labs, Kenyi, Red Zebras, and other common Africans.
However, it will be well worth the work - African Cichlid tanks look GREAT!