Martin Lee, Wallis John D, Guziak Milena, Maksymiw Peter, Konalian-Kempf Florence, Christian Anthony, Nakatsuji Shin'ichi, Yamada Jun'ichi, Akutsu Hiroki
School of Science and Technology, Nottingham Trent University, Clifton Lane, Nottingham, NG11 8NS, UK.
Graduate School of Material Science, University of Hyogo, Kamigori-cho, Ako-gun, Hyogo 678-1297, Japan.
Dalton Trans. 2017 Mar 27;46(13):4225-4234. doi: 10.1039/c6dt04645b.
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 I and I. Enantiomorphic 6 : 6 donor : I 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.
基于手性四硫富瓦烯（TTF）的给体分子双（2'-羟丙基硫基）（乙二硫基）四硫富瓦烯（BHPT - EDT - TTF）与多碘化物阴离子I和I形成了对映纯的R，R和S，S自由基阳离子盐。由R，R或S，S给体生长的对映体6∶6给体∶I相是半导体，其激活能分别相似，为0.24 - 0.30 eV和0.22 - 0.23 eV，并且包含三个独特的面对面给体对，其相对取向由侧链构象和氢键决定。在相同条件下的外消旋材料产生了一种绝缘的中心对称相，其中R，R和S，S给体阳离子以面对面的对与八碘化物二阴离子配对，并且对映体之间存在约3∶1的无序。对映纯的BHPT - EDT - TTF产生了另外两种绝缘结晶相，其组成为与三碘化物的2∶2和与八碘化物的2∶1。
