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Article Dans Une Revue Chemistry - A European Journal Année : 2013

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

Résumé

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 derivs., (EDT-TTFI2)2(TCNQFn), n=0-2, which exhibit variable degrees of ionicity. The iodinated tetrathiafulvalene deriv., EDT-TTFI2, assocs. with tetracyanoquinodimethane (TCNQ) and its derivs. of increasing redn. potential (TCNQF, TCNQF2) through highly directional C-I***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 TCNQF2 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 neutral-ionic conversion takes place upon cooling. A correlation between the degree of charge transfer and the C-I***N≡C halogen-bond strength is established from the comparison of the structures of the three isostructural complexes at temps. 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 temp. dependence of its magnetic susceptibility and the stretching modes of the C≡N groups.

Dates et versions

hal-01151717 , version 1 (13-05-2015)

Identifiants

Citer

Julien Lieffrig, Olivier Jeannin, Arkadiusz Fra, Arkadiusz Frackowiak, Iwona Olejniczak, et al.. Charge-Assisted Halogen Bonding: Donor–Acceptor Complexes with Variable Ionicity. Chemistry - A European Journal, 2013, 19 (44), pp.14804 - 14813. ⟨10.1002/chem.201302507⟩. ⟨hal-01151717⟩
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