Complex formation of ethylenedioxyethylenedithiotetrathiafulvalene (EDOEDT-TTF : EOET) and its self-assembling ability
Complex formation of ethylenedioxyethylenedithiotetrathiafulvalene (EDOEDT-TTF : EOET) and its self-assembling ability
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DOI：
10.1039/b110605h
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发表时间：
2002-05
影响因子：
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通讯作者：
G. Saito;H. Sasaki;T. Aoki;Y. Yoshida;A. Otsuka;H. Yamochi;O. Drozdova;K. Yakushi;H. Kitagawa;T. Mitani
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文献类型：
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作者：
G. Saito;H. Sasaki;T. Aoki;Y. Yoshida;A. Otsuka;H. Yamochi;O. Drozdova;K. Yakushi;H. Kitagawa;T. Mitani
以双乙撑二氧乙烯二硫代四硫富瓦烯（EDOEDT-TTF或EOET）和双乙撑二硫代四硫富瓦烯（BEDT-TTF或ET）的杂化分子为基础，制备了36种给体（D）-受体（A）型电荷转移（CT）固体。固体中的第一CT吸收带相对于供体和受体分子之间的第一氧化还原电位差（ΔE）的曲线图将复合物分为五组，A：具有部分CT状态和分离堆叠的高导电CT复合物，B：具有交替堆叠的部分离子CT绝缘体，C：基本上中性的笼形复合物，D：具有交替堆叠的中性CT绝缘体，以及E：完全离子绝缘体。与一维有机金属（如1 ∶ 1 TTF-TCNQ体系）相比，A组分布在广泛的ΔE范围内。这表明这组中的EOET配合物具有高的电子维数所产生的自聚集的EOET分子的方式类似于BO的。然而，EOET分子的自组装能力不如BO分子明显，从而使A族中的许多络合物发生金属-绝缘体转变。降低的自组装能力还提供了（MeO）2 TCNQ、BTDA-TCNQ（B组）和对碘苯胺（C组）络合物的交替堆叠。用球形C60制备了两种结构不同的复合物（D组），一种含有凹型EOET分子和一维C60柱，另一种含有平面EOET和二维C60层。F_4TCNQ配合物（E组）在低于7 K时表现出反铁磁有序性，介于（BO）（F_4TCNQ）（5.4K）和（ET）（F_4TCNQ）（14 K）之间.
36 kinds of donor(D)–acceptor(A) type charge transfer (CT) solids were prepared based on ethylenedioxyethylenedithiotetrathiafulvalene (EDOEDT-TTF or EOET), which is a hybrid molecule of bis(ethylenedioxy)-TTF (BEDO-TTF or BO) and bis(ethylenedithio)-TTF (BEDT-TTF or ET). A plot of the first CT absorption bands in solids against the difference in first redox potential between donor and acceptor molecules (ΔE) classified the complexes into five groups, A: highly conductive CT complexes with partial CT state and segregated stacks, B: partially ionic CT insulators with alternating stacks, C: essentially neutral clathrate complexes, D: neutral CT insulators with alternating stacks, and E: completely ionic insulators. Group A is spread out over an extensive ΔE range compared to one-dimensional organic metals such as the 1 ∶ 1 TTF–TCNQ system. This indicates that the EOET complexes among this group have a high electronic dimensionality arising from the self-aggregation of the EOET molecules in a fashion similar to the BO ones. However, the self-assembling ability of the EOET molecules is less pronounced than that of the BO ones, thereby giving a metal–insulator transition for many complexes among Group A. The reduced self-assembling ability also affords alternating stacks in (MeO)2TCNQ, BTDA-TCNQ (Group B) and p-iodanil (Group C) complexes. Two structurally distinct complexes were prepared with spherical C60 (Group D), one containing concave EOET molecules and one-dimensional C60 columns, and the other planar EOET and two-dimensional C60 layers. The F4TCNQ complex (Group E) exhibits an antiferromagnetic ordering below 7 K, which is intermediate between those in (BO)(F4TCNQ) (5.4 K) and (ET)(F4TCNQ) (14 K).