Charge transfer complexes and radical cation salts of chiral methylated organosulfur donors

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Yang, S., Pop, F., Melan, C., Brooks, A.C., Martin, L. ORCID: 0000-0002-5330-5700, Horton, P., Auban-Senzier, P., Rikken, G.L.J.A., Avarvari, N. and Wallis, J.D. ORCID: 0000-0001-7259-8783, 2014. Charge transfer complexes and radical cation salts of chiral methylated organosulfur donors. CrystEngComm, 16 (19), pp. 3906-3916. ISSN 1466-8033

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Official URL: http://dx.doi.org/10.1039/c3ce42539h

Abstract

The single crystal X-ray structure of the all-axial conformer of the (R,R,R,R) enantiomer of the chiral donor tetramethyl-BEDT-TTF (TM-BEDT-TTF) was described and compared to the all-equatorial conformer. (S,S,S,S)-Tetramethyl-BEDT-TTF formed crystalline 1 : 1 complexes with TCNQ and TCNQ-F4, as well as a THF solvate of the TCNQ complex. Donors bis((2S,4S)-pentane-2,4-dithio)tetrathiafulvalene and (ethylenedithio)((2S,4S)-pentane-2,4-dithio)tetrathiafulvalene, which contain seven-membered rings bearing chirally oriented methyl groups, only formed complexes with TCNQ-F4. The TCNQ-F4 complexes contain planar organosulfur systems, in contrast to the TCNQ complexes in which there is minimal charge transfer. A variety of crystal packing modes were observed. Electrocrystallization experiments with both enantiomers and the racemic form of tetramethyl-BEDT-TTF afforded mixed valence radical cation salts with the AsF6 and SbF6 anions formulated as (TM-BEDT-TTF)2XF6 (X = As, Sb). Electrical conductivity was only found in one charge transfer complex, while the radical cation salts are all semiconducting.

Item Type:

Journal article

Publication Title:

CrystEngComm

Creators:

Yang, S., Pop, F., Melan, C., Brooks, A.C., Martin, L., Horton, P., Auban-Senzier, P., Rikken, G.L.J.A., Avarvari, N. and Wallis, J.D.

Publisher:

Royal Society of Chemistry

Place of Publication:

Cambridge

Date:

2014