By using the brakes whilst riding, they don’t remain ‘open’ long enough to allow the air to move…by leaving them overnight (with the reservoir as the highest point of the system), you give the air enough time to work it;s way up the hose to the reservoir. This doesn’t get rid of all air but gets rid of a huge chunk.
Thing to be aware of is Dot fluid is hydrascopic so rather than leaving the top cap off and the fluid exposed, I tend to lock the lever down and in the morning, remove the top cap, then release the lever…normally if I have air in the system I can see a drop in the fluid level…which I then simply top up and put top cap back on.
Sort of the same reason why reverse-bleeding works well – it forces the air to move along with the flow of the fluid and ensures the air is forced up and out the system (air rises naturally).