Interplay of Halogen and π–π Charge-Transfer Bondings in Intermolecular Associates of Bromo- or Iododinitrobenzene with Tetramethyl‑<i>p</i>‑phenylenediamine

Two modes of intermolecular interactions (halogen and π–π charge-transfer bonding) between bromo- or iododinitrobenzene (XDNB) and tetramethyl-<i>p</i>-phenylenediamine (TMPD) are compared. X-ray crystallography revealed that TMPD·XDNB cocrystals comprise alternating donors/acceptors stacks formed by π-bonded (cofacial) TMPD and XDNB molecules. These structures also show two-point (C–X···O–N) halogen bonding between XDNB molecules resulting in formation of (XDNB)₂ dimers. In solutions, XDNB and TMPD molecules formed 1:1 complexes showing strong absorption bands near 550 nm which followed the same Mulliken correlation as the associates of TMPD with the (halogen-free) nitro- and cyanobenzenes. In accord with the experimental data, density functional theory calculations with the M062X functional showed that TMPD·XDNB associates formed via π–π charge-transfer bonding are more stable (by 6–12 kcal/mol) than their halogen-bonded analogues. If XDNB is replaced with iodo- or bromoperfluorinated benzenes, or TMPD is replaced with pyridine, the energy gap between the π–π and halogen-bonded associates decreased. The analysis of the molecular-orbital interactions and surface electrostatic potentials of the interacting species indicated that charge-transfer contributions represent a critical component which determines variations of the strength of halogen bonding in these systems