Molecular and Crystal Structure Diversity, and Physical Properties of Tetrathiafulvalene Derivatives Substituted with Various Aryl Groups through Sulfur Bridges
Molecular and Crystal Structure Diversity, and Physical Properties of Tetrathiafulvalene Derivatives Substituted with Various Aryl Groups through Sulfur Bridges
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通过硫桥取代各种芳基的四硫富瓦烯衍生物的分子和晶体结构多样性及物理性质
DOI：
10.1002/chem.201301819
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发表时间：
2013-09-09
影响因子：
4.3
通讯作者：
Shao, Xiangfeng
中科院分区：
文献类型：
--
作者：
Sun, Jibin;Lu, Xiaofeng;Shao, Xiangfeng
建立了通过硫桥连接芳基的四噻吩（TTF）衍生物（TTF-1-TTF-47）库。外围芳基对所得ttf的电子和晶体学性质都有显著影响。这些TTF在400-500nm处表现出较宽的吸收带，这是由于芳香基与TTF中心核之间的分子内电荷转移跃迁引起的，它们的首次氧化还原电位随着芳香基吸电子能力的增加而增加。在它们的晶体结构（22个例子）中，中央TTF核采用各种构象，包括椅子、半椅子、船形和平面构象。此外，外围芳基相对于中心TTF核心表现出多种排列模式，这是由于它们围绕硫桥的两个CS键旋转造成的。这些ttf的填充基序取决于芳基的性质和它们的空间排列模式。在分子间范德华力和芳基之间以及芳基与TTF核之间的相互作用的驱动下，TTF采用不同的填充结构。典型的例子是非手性分子TTF-14，通过分子间原子紧密接触形成螺旋链堆叠。此外，这些ttf的分子几何形状和填充基序对环境变化非常敏感，如TTF-28，它在不同的结晶条件下采用了三种不同的晶体修饰，具有不同的分子几何形状和堆叠模式。这项工作表明，这些ttf是潜在的候选电子材料，以及超分子组装的功能构建块。
A library of tetrathiafulvalene (TTF) derivatives (TTF-1-TTF-47) bearing aryl groups attached through sulfur bridges has been created. The peripheral aryl groups exert a significant influence on both the electronic and crystallographic properties of the resulting TTFs. These TTFs display broad absorption bands at 400-500nm caused by intramolecular charge-transfer transitions between the aryl groups and central TTF core, and their first redox potentials increase with increasing electron-withdrawing ability of the aryl groups. In their crystal structures (22 examples), the central TTF cores adopt various conformations, including chair, half-chair, boat, and planar conformations. Moreover, the peripheral aryl groups exhibit multiple alignment modes with respect to the central TTF core, caused by their rotation about the two CS bonds of the sulfur bridges. The packing motifs of these TTFs depend on both the nature of the aryl groups and their spatial alignment modes. Driven by intermolecular van der Waals forces and - interactions between the aryl groups and between the aryl groups and the TTF core, these TTFs adopt various packing structures. As a typical example, TTF-14, an achiral molecule, adopts a helical chain stack through intermolecular atomic close contacts. Moreover, the molecular geometries and packing motifs of these TTFs are sensitive to environmental variation, as exemplified by TTF-28, which adopts three distinct crystal modifications with diverse molecular geometries and stacking modes under different crystallization conditions. This work indicates that these TTFs are potential candidates as electronic materials, as well as functional building blocks for supramolecular assembly.