Weaving Nanoscale Cloth through Electrostatic Templating

Here we disclose a simple route to nanoscopic 2D woven structures reminiscent of the methods used to produce macroscopic textiles. We find that the same principles used in macroscopic weaving can be applied on the nanoscale to create two-dimensional molecular cloth from polymeric strands, a molecular thread. The molecular thread is composed of Co6Se8(PEt3)4L2 superatoms that are bridged with L = benzene bis-1,4-isonitrile to form polymer strands. As the superatoms that make up the polymer chain are electrochemically oxidized, they are electrostatically templated by a nanoscale anion, the tetragonal Lindqvist polyoxometalate Mo6O192–. The tetragonal symmetry of the dianionic template creates a nanoscale version of the box weave. The crossing points in the weave feature π-stacking of the bridging linker. By examining the steps in the weaving process with single crystal X-ray diffraction, we find that the degree of polymerization at the crossing points is crucial in the cloth formation. 2D nanoscale cloth will provide access to a new generation of smart, multifunctional materials, coatings, and surfaces.本文报道了一条制备纳米级二维编织结构的简易路线，其制备思路借鉴了宏观纺织品的编织方法。我们发现，宏观编织所采用的核心原理可拓展至纳米尺度，以聚合物链（即分子线）为原料制备二维分子织物。该分子线由Co6Se8(PEt3)4L2超原子（superatoms）组装而成，以L=苯-1,4-二异氰作为桥连配体，进而形成聚合物链。当构成聚合物链的超原子发生电化学氧化时，它们会被一种纳米级阴离子——四方Lindqvist型多金属氧酸盐（polyoxometalate）Mo6O19^2–——进行静电模板化调控。该双阴离子模板的四方对称性，构建出了纳米尺度的盒状编织结构。该编织结构的交叉点以桥连配体的π堆积相互作用为典型特征。通过单晶X射线衍射（single crystal X-ray diffraction）表征编织过程的各个阶段，我们发现，交叉点处的聚合度对分子织物的形成至关重要。二维纳米织物将为新一代智能多功能材料、涂层及表面材料的研发提供全新的可行途径。