Enantiopure and racemic radical-cation salts of bis(2'-hydroxylpropylthio)(ethylenedithio)TTF with polyiodide anions

Lee Martin; John D Wallis; Milena Guziak; Peter Maksymiw; Florence Konalian-Kempf; Anthony Christian; Shin'ichi Nakatsuji; Jun'ichi Yamada; Hiroki Akutsu

doi:10.1039/c6dt04645b

Enantiopure and racemic radical-cation salts of bis(2'-hydroxylpropylthio)(ethylenedithio)TTF with polyiodide anions

Dalton Trans. 2017 Mar 27;46(13):4225-4234. doi: 10.1039/c6dt04645b.

Authors

Lee Martin¹, John D Wallis¹, Milena Guziak¹, Peter Maksymiw¹, Florence Konalian-Kempf¹, Anthony Christian¹, Shin'ichi Nakatsuji², Jun'ichi Yamada², Hiroki Akutsu³

Affiliations

¹ School of Science and Technology, Nottingham Trent University, Clifton Lane, Nottingham, NG11 8NS, UK. lee.martin@ntu.ac.uk.
² Graduate School of Material Science, University of Hyogo, Kamigori-cho, Ako-gun, Hyogo 678-1297, Japan.
³ Graduate School of Material Science, University of Hyogo, Kamigori-cho, Ako-gun, Hyogo 678-1297, Japan and Department of Chemistry, Graduate School of Science, Osaka University, 1-1 Machikaneyama-cho, Toyonaka, Osaka 560-0043, Japan.

PMID: 28280818
DOI: 10.1039/c6dt04645b

Abstract

The chiral TTF-based donor molecule bis(2'-hydroxylpropylthio)(ethylenedithio)tetrathiafulvalene (BHPT-EDT-TTF) has produced enantiopure R,R and S,S radical-cation salts with polyiodide anions I₃^- and I₈^2-. Enantiomorphic 6 : 6 donor : I₃ phases grown from either the R,R or S,S donor are semiconducting with similar activation energies of 0.24-0.30 eV and 0.22-0.23 eV, respectively, and contain three unique face-to-face donor pairs whose relative orientation is determined by side chain conformations and hydrogen bonding. Racemic material under the same conditions gave an insulating centrosymmetric phase with R,R and S,S donor cations in a face-to-face pair partnered with an octaiodide dianion, and with a ca. 3 : 1 disorder between the enantiomers. Enantiopure BHPT-EDT-TTF yielded two further insulating crystalline phases of composition 2 : 2 with triiodide and 2 : 1 with octaiodide.