Charge-Assisted Halogen Bonding: Donor-Acceptor Complexes with Variable Ionicity

Charge-assisted halogen bonding is unambiguously revealed from structural and electronic investigations of a series of isostructural charge-transfer complexes derived from iodinated tetrathiafulvalene and tetracyanoquinodimethane derivatives, (EDT-TTFI2)(2)(TCNQF(n)), n=0-2, which exhibit variable degrees of ionicity. The iodinated tetrathiafulvalene derivative, EDT-TTFI2, associates with tetracyanoquinodimethane (TCNQ) and its derivatives of increasing reduction potential (TCNQF, TCNQF(2)) through highly directional C-I center dot center dot center dot N=C halogen-bond interactions. With the less oxidizing TCNQ acceptor, a neutral and insulating charge-transfer complex is isolated whereas with the more oxidizing TCNQF(2) acceptor, an ionic, highly conducting charge-transfer salt is found, both of 2:1 stoichiometry and isostructural with the intermediate TCNQF complex, in which a neutralionic conversion takes place upon cooling. A correlation between the degree of charge transfer and the C-I center dot center dot center dot N=C halogen-bond strength is established from the comparison of the structures of the three isostructural complexes at temperatures from 300 to 20 K, thus demonstrating the importance of electrostatics in the halogen-bonding interaction. The neutral-ionic conversion in (EDT-TTFI2)(2)(TCNQF) is further investigated through the temperature dependence of its magnetic susceptibility and the stretching modes of the C=N groups.