31P-31P spin-spin coupling constants for pnicogen homodimers

► The pnicogen bond stabilizes (PH2X)2 with X = F, OH, NC, NH2, CCH, CN, CH3, H, BH2. ► Complex binding energies arising from the P⋯P bond range from 7 to 34 kJ mol−1. ► 31P-31P spin-spin coupling constants characterize the pnicogen bond.