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.