North Carolina State
Syracuse is Pitt's primary partner meaning the school from the other division that they will play every year.
While there will be no divisions in basketball, Pitt's primary partner will be Maryland, which means they will play them home and home every year. That will be good for recruiting purposes since Pitt often recruits in the Maryland area.
For football recruiting, playing against Virginia and Virginia Tech every year will be good because it opens up a fertile recruiting area.