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Charge-assisted Halogen Bonding: Donor-Acceptor Complexes With Variable Ionicity

Charge-assisted Halogen Bonding: Donor-Acceptor Complexes With Variable Ionicity

Julien Lieffrig, Olivier Jeannin, Arkadiusz Frąckowiak, Iwona Olejniczak, Roman Świetlik, Slimane Dahaoui, Emmanuel Aubert, Enrique Espinosa, Pascale Auban-Senzier, Marc Fourmigué

Chemistry. 2013 Oct 25;19(44):14804-13.

PMID: 24591214

Abstract:

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, 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 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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP40210842	Tetrathiafulvalene 7,7,8,8-tetracyanoquinodimethane salt		40210-84-2	Price

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