有机功能材料籍由有机分子通过分子间作用组装而成，因此合成具有特殊本征性能及组装功能的有机分子是有机功能材料研究的基础及创新点。本项目以四硫富瓦烯（TTF）为母体，在其外围以硫原子为桥联，引入具有不同电子效应、对称性及组装功能基团的芳香环。目标分子的独特性在于扩展了体系的pi-共轭结构；而且芳基围绕C-S键的旋转/振动自由度，使得分子的构型能够受物理或化学环境之诱导而自发调整，譬如呈碗状构型。利用分子间pi-pi作用、配位作用、电荷转移以及芳基围绕TTF骨架旋转/振动所形成的分子内禀空腔，通过电化学结晶及多组份扩散等方法实现TTF衍生物的混合结晶，及其与过渡金属、富勒烯、杂多酸等功能组分的可控超分子组装和功能熔合。以期得到具有特殊组装结构（包络复合物、金属-有机框架结构、过渡金属链）和性能(导电、磁性、吸附、催化)的有机功能材料。在阐明材料的构效关系之基础上，拓展组装材料在分子器件中的应用。

Organic functional materials are based on the assembly of organic molecules via intermolecular interactions. Therefore, the gateway for the development of organic functional materials is to design and synthesize organic molecules having unique features on both electronic and crystallographic aspects. In the present proposal, we aim at the design, synthesis, and supramolecular assembly diversity of functional organic molecules possessing conformation self-modulation ability induced by circumstance variation. The target molecules are aryl-substituted/fused tetrathiafulvalene (TTF) derivatives, for which the aryls and TTF framework are connected via sulfur atom bridge. The key characters of these molecules are (1) extention of pi-conjugation result from aryls, and (2) enhancement of molecular internal freedom caused by the rotation/vibration of aryls around two C-S bonds. The target molecules will be synthesized through the copper-catalyzed C-S coupling reaction between aryl iodides and (TBA)2[Zn(DMIT)2], and by successive phosphate-mediated coupling reaction. The supramolecular assembly of the resulting TTF derivatives and other functional components, such as fullerene, transition metals, rare earth metals, and heteropoly acid (HPA) will be carried out. The driving forces for supramolecular assembly are hydrogen-bond, pi-pi interaction, charge-transfer, and coordination between TTF derivatives and counter components. Especially, the rotation/vibration of aryls around two C-S bonds would make the peripheral aryls and central TTF core together form a bowl-like cavity under certain conditions, which is capable to encapsulate guest molecules having appropriate size and symmetry, for example, fullerene and HPA. The target materials are conducting inclusion complex with fullerene, conducting/magnetic inclusion complexes with HPA, conducting/magetic metal-organic framework (MOF), one-dimensional magnets of transition metal, and co-existence of conduction (TTF stacks) and magnetism (transition metal sheet). Futher investigation is directed to the fabrication of molecular electronic devices based on the above supramolecular materials.