由TTF自由基正离子和Keggin型杂多酸组成的蜂窝状自组装材料

Honeycomb supramolecular frameworks composed of TTF cation radical and Keggin-type polyoxometalate

以硫桥连硒酚基取代TTF(tse)为有机组分,Keggin型杂多酸阴离子(pma)为无机组分,利用分级组装的方法制备了三维纳米材料,其分子式为[(tse)+·]3[(pma)3-](CH2Cl2)。通过光谱,电化学,动态光散射,扫描电子显微镜(SEM)和X-单晶衍射等对组装过程进行了研究。结合研究结果和强弱不同的作用力在分级组装中的优先顺序,自组装经过了如下过程:tse首先在酸的作用下形成正离子自由基,然后通过静电作用与磷钼酸根离子结合为有机—无机砌块;随后tse之间通过多重分子间作用力结合形成二维纳米面;最后纳米面之间通过分子间作用力使材料的堆积向三维延伸,形成了具有六棱柱空腔的三维蜂窝状自组装材料。

Keggin-type phosphomolybdic acid（H3PMo12O40） promotes the formation of cation radical of tetra（thienylthio）-tetrathiafulvalene（tse）,and it consequently resultes in a cation radical complex[（tse）^＋ ·]3[（pma）3-]（CH2Cl2）,which shows self-assembly in solution and forms microcrystals.The molecular level structure of microtube is evaluated by X-ray diffraction analysis,which reveals the crystal is produced via various non-convalent interactions in the hierarchical assembly process：the electrostatic interactions between（tse）^＋ ·and（pma）3-afford an organic-inorganic hybrid triangular nanocluster[（tse）^＋□]3[（pma）3-]as the building block; the strong %-%interactions between（tse）^＋ ·result in the cluster-based twodimensional honeycomb nanosheet; the van der Waals forces between the nanosheets lead to the propagation along the third direction to form three-dimensional supramolecular framework possessing nano-sized channel.