By studying the (109)Xe→(105)Te→(101)Sn superallowed α-decay chain, we observe low-lying states in (101)Sn, the one-neutron system outside doubly magic (100)Sn. We find that the spins of the ground state (J=7/2) and first excited state (J=5/2) in (101)Sn are reversed with respect to the traditional level ordering postulated for (103)Sn and the heavier tin isotopes. Through simple arguments and state-of-the-art shell-model calculations we explain this unexpected switch in terms of a transition from the single-particle regime to the collective mode in which orbital-dependent pairing correlations dominate.