Silicone does work, you just need to be pragmatic about bead size, and wait for it to cure before submerging!
To explain:
— standard aquarium silicone adhesive is a Room Temperature Vulcanizing (RTV) formula, which means it cures at room temp, via exposure to atmospheric humidity! If you make the blobs of silicone holding the rock too large (<3/4”-1” diameter), you’ll ends up having to wait weeks for it to cure!
— RTV silicone typically has petroleum distillates in the formula, in addition to acetic acid… these off-gas over time as the silicone hardens (cures)… you want the silicone to be fully cured before you submerge it, which ideally will be 1-3 weeks after silicone application (depending on how much silicone is used/blob size)!
As an alternative, you could always silicone a bracket shaped piece(s) of glass or acrylic to the overflow box, then use the likes of 3/8”-1/2” acrylic rod like a nail to hold your rock structure to this bracket! (This would be best-bet if using live rock for the structure, as it avoids the part where the rock sits dry for >=1 week straight!)