When I try to assign an empty automation slot to it, it simply just won't allow me, any help?
It looks like you are trying to assign something to the Bend, this is already hard coded and assigned to the pitchwheel, so you can't assign another MIDI CC to that.
What DAW? in Logic, I use the PainoRoll automation to draw it in, but if I remember correctly it also gets drawn in by moving those sliders. Of course that is after you've recorded your midi part/s.
FL Studio.