Homo- and heterochiral dimers (PHFX)2, XÂ =Â Cl, CN, CH3, NC: To what extent do they differ?

► Optically active molecules PHFX give rise to homo- and heterochiral dimers (PHFX)2. ► Properties of (PHFX)2 depend primarily on X and Z in the linear Z-P⋯P-Z alignment. ► Binding energies of corresponding C2 and Ci dimers differ by only 1-3 kJ/mol. ► P-P distances in Ci isomers tend to be shorter than in corresponding C2 isomers. ► 1pJ(P-P) coupling constants fail to distinguish between corresponding isomers.