Synthesis, crystal structure and properties of the semiconducting molecular charge-transfer salt (bedt-ttf)2Ge(C2O4)3·PhCN [bedt-ttf=bis(ethylenedithio)tetrathiafulvalene]
Synthesis, crystal structure and properties of the semiconducting molecular charge-transfer salt (bedt-ttf)2Ge(C2O4)3·PhCN [bedt-ttf=bis(ethylenedithio)tetrathiafulvalene]
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半导体分子电荷转移盐(bedt-ttf)2Ge(C2O4)3·PhCN[bedt-ttf=双(乙撑二硫)四硫富瓦烯]的合成、晶体结构及性能
DOI：
10.1039/a905723d
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发表时间：
1999
影响因子：
--
通讯作者：
K. Yakushi
中科院分区：
文献类型：
--
作者：
Lee Martin;S. Turner;P. Day;P. Guionneau;J. Howard;M. Uruichi;K. Yakushi
本文报道了一种新的含三（邻氨基）锗（IV）负离子的bedt-ttf电荷转移盐的合成、晶体结构和物理性质。在（NH_4）_2Ge（C_2O_4）_3·2H_2O存在下，中性bedt-ttf在PhCN溶液中的电化学氧化生成（bedt-ttf）_2Ge（C_2O_4）_3·PhCN晶体。在296（2）K和120（2）K下解出了晶体结构。与众所周知的bedt-ttf的三（重氮）-金属（III）盐相反，该结构不包含bedt-ttf阳离子和三（重氮）金属阴离子的交替层，而是由面对面的bedt-ttf二聚体的“棋盘”排列组成，其中[Ge（C2 O 4）3]2-散布有溶剂分子层。每个bedt-ttf分子具有接近+1的电荷，这是根据CC和C-S键长之间的经验关系估计的，并且这些电荷与拉曼光谱相关。正如预期的存在下，强烈二聚（bedt-ttf+）2单位的盐是一个半导体之间的300和120 K的低活化能为0.127 eV。
The synthesis, crystal structure and physical properties of a new bedt-ttf charge transfer salt containing the tris(oxalato)germanium(IV) anion are described and interpreted. Electrochemical oxidation of neutral bedt-ttf in the presence of (NH4)2Ge(C2O4)3·2H2O in PhCN solution yields crystals of (bedt-ttf)2Ge(C2O4)3·PhCN. The crystal structure has been solved at 296(2) and at 120(2) K. In contrast to the well known tris(oxalato)-metallate(III) salts of bedt-ttf, the structure does not contain alternating layers of bedt-ttf cations and tris(oxalato)metallate anions, but consists of a ‘checker board’ arrangement of face-to-face bedt-ttf dimers with [Ge(C2O4)3]2– interspersed by layers of solvent molecules. Each bedt-ttf molecule has a charge close to +1, which is estimated from the empirical relationship between CC and C–S bond lengths and these charges are correlated with Raman spectra. As expected from the presence of strongly dimerised (bedt-ttf+)2 units the salt is a semiconductor between 300 and 120 K with a low activation energy of 0.127 eV.