An alternating conduction-insulation "molecular fence" model from fluorinated metallopolymers.

Introducing fluoroalkyl chains into metallopolymers is a prerequisite to studying the self-organization effect of fluoroalkyl chains and their structure-property relationship. In this work, we present a fluorinated metallopolymer to build an alternating conduction-insulation "molecular fence" model synthesized by the coordination of Ru(II) and a bis-terpyridine-end-capped-phenyl (BTP) ligand modified with fluoroalkyl chains. Taking advantage of scanning tunneling microscopy (STM), a well-aligned periodic linear layered structure is observed clearly, which provides the most direct visualization of the self-organization effect of fluoroalkyl chains for the first time. In addition, combining ultraviolet-visible (UV-vis) absorption spectroscopy and theoretical calculations, we find that fluoroalkyl chains demonstrate a septation effect between two adjacent metallopolymer chains and further restrain the occurrence of interchain charge-transfer transition (ICCT) due to their closed packed structure. This "molecular fence" model can provide a novel route for electron conduction in molecular networks and guide potential applications in the materials science field.