It's a very nice idea, and certainly a problem for longer treks, as you pointed out. But here's the problems
1. The energy required to pump the room down to near vacuum means a larger, heavier pump/motor. This means heavier deadweight, thus more fuel required, plus less space. But this isn't the main problem, especially on so-called "Large scale stations".
2. The big problem is the time it takes. What are you gaining by waiting in the suit inside the room while the air pumps out? An average person uses approximately .5 Liters of air per breath at normal conditions. (and at standard psi, its somewhat less at the 4.3 psi suit pressure, though somewhat higher in O2 concentration). But let's say .5L per breath. Thats roughly 7.5 L of air per minute, 450 L per hour.
They already spend nearly an hour decompressing down to the nominal suit pressure (after several hours decompressing down to the ~10 psi I mentioned before) So you would need to balance between the air used just waiting versus venting the 5psi compartment. You waste both time and air depressurizing the compartment, whereas you can vent the air you would lose waiting anyway and spend the time and oxygen on something worthwhile.
I haven't done any of the calculations, but I'm going to bet it's either close, or it's deemed more valuable to have them outside breathing oxygen, than having the astronauts sitting inside wasting that oxygen in an attempt to save air that is mostly nitrogen.