The hyperfine structures of the odd-even 51−63Mn atoms (N = 26 − 38) were measured using bunched beam collinear laser spectroscopy at ISOLDE, CERN. The extracted spins and magnetic dipole moments have been compared to large-scale shell-model calculations using different model spaces and effective interactions. In the case of 61,63Mn, the results show the increasing importance of neutron excitations across the N = 40 subshell closure, and of proton excitations across the Z = 28 shell gap. These measurements provide the first direct proof that proton and neutron excitations across shell gaps are playing an important role in the ground state wave functions of the neutron-rich Mn isotopes.