Can I create a totem-pole structure by using two optocouplers?
You can, but you wouldn't want to connect the bases together like that.

If you're just passing a binary signal, as implied by your LED drive circuit, just leave the bases open as usual.

If you're interested in analog signals, then you would connect the bases to a suitable bias network that establishes a quiescent operating point for the transistors.

But there's rarely a good reason to use two optoisolators when a single one followed by a suitable buffer/driver would do the job.