They could have at any time but they haven’t. Even in the Covid season, there was no serious discussion of leaving the ACC affiliation for the B1G or the SEC although they could easily afford the exit fee. I don’t think people understand how much Notre Dame dislikes the B1G. They really like the current setup with the ACC.
Phillips is looking for a big time move to show the ACC is stable. Right now there is no other conference that looks as close to disappearing like the Pac12 as the ACC. Notre Dame wants to keep its tv deal with NBC and have scheduling flexibility but they also don’t want the ACC to disappear. I would not be surprised if ND repays the favor of the Covid season by agreeing to a drug deal with Phillips. Phillips announces that ND has “officially” joined the ACC but in reality Notre Dame remains independent in all but name (they get to keep NBC contract, still have more scheduling flexibility than other ACC teams, but also have to play 7 or 8 ACC teams instead of 5). It would obviously just be window dressing, but people have a short attention span. The headline will read "Notre Dame drops independence for the ACC"and it gets a ton of buzz and makes Phillips appear like a strong commissioner. Few people are going to dig into the particulars. It doesn’t bring more money to the ACC so the underlying problems don’t change, but right now the key issue is perception and the drug deal buys Phillips and the ACC some time.
Again I think the most likely outcome of all this is the ACC slims down and increases quality - it " adds" ND, and sends a few teams (Louisville, Syracuse, possibly NC St) to the Big 12 without them having to pay the exit fee to increase the payout to the remaining ACC teams, espn agrees to up the payouts because of the market competitiveness clause in the contract, and most importantly, the ACC does a massive overhaul of the revenue distribution so the teams that get the best ratings get more money.
On paper the top teams in the ACC will make reasonably close to what the P2 makes (not the entire conference just the top teams). FSU and Clemson drop their complaints and can live with the ACC arrangement for a few more years knowing the one giant mega conference is on the horizon.