Chiral Radical-Cation Salts of BEDT-TTF Containing a Single Enantiomer of Tris(oxalato)aluminate(III) and -chromate(III)
Chiral Radical-Cation Salts of BEDT-TTF Containing a Single Enantiomer of Tris(oxalato)aluminate(III) and -chromate(III)
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含有三(草酸)铝酸(III)和铬酸(III)单一对映体的BEDT-TTF手性自由基阳离子盐
DOI：
10.1002/ejic.201500092
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发表时间：
2015
影响因子：
2.3
通讯作者：
W. Clegg
中科院分区：
文献类型：
--
作者：
Lee Martin;H. Akutsu;P. Horton;M. Hursthouse;R. Harrington;W. Clegg
BEDT-TTF的自由基阳离子盐与手性阴离子提供了在相同的分子材料中结合手性和电导率的机会。本文报道了（BEDT-TTF）3NaAl(C2O4)3·硝基甲烷和（BEDT-TTF）3(NH4)0.83Cr1.17(C2O4)3·硝基甲烷两种盐类。前者在P21空间群中结晶，后者在P212121空间群中结晶。单独使用硝基甲烷作为电结晶的电解质不会产生晶体，但加入手性(R)-(-)-香豆酮通过手性诱导，从外消旋三（草酸）铝酸盐（III）和三（草酸）铬酸盐起始材料中产生这两种新的BEDT-TTF手性自由基阳离子盐晶体。这些盐中的蜂窝状阴离子层含有三（草酸）金属酸酯的单一对映体，并产生比三（草酸）金属酸酯家族中超导β″盐中发现的更小的六角形空腔，这使得更小的溶剂（如硝基甲烷）优先被包括在内。铬盐具有阴离子层的非化学计量组成，对供体层提供电子掺杂效应。
Radical-cation salts of BEDT-TTF with chiral anions provide the opportunity to combine chirality with conductivity in the same molecular material. We report here two salts, (BEDT-TTF)3NaAl(C2O4)3·nitromethane and (BEDT-TTF)3(NH4)0.83Cr1.17(C2O4)3·nitromethane. The former crystallises in space group P21 and the latter in P212121. The use of nitromethane alone as the electrolyte for electrocrystallisation produces no crystals, but the addition of chiral (R)-(–)-carvone yields crystals of these two new chiral radical-cation salts of BEDT-TTF through chiral induction from racemic tris(oxalato)aluminate(III) and tris(oxalato)chromate starting materials. The honeycomb anion layers in these salts contain a single enantiomer of tris(oxalato)metallate and creates hexagonal cavities that are smaller than those found in the superconducting β″ salts in this tris(oxalate)metallate family, which gives preference for smaller solvents to be included, such as nitromethane. The chromium salt has a non-stoichiometric composition of the anion layer, which provides an electron doping effect to the donor layer.
一系列分子电荷转移盐中供体堆积排列的上层结构
影响因子：
4.9
作者：
K.Sugiyama;et al.;H. Akutsu
通讯作者：
H. Akutsu