Synthesis and metalation of polycatechol nanohoops derived from fluorocycloparaphenylenes.

Due to their unique topology and distinct physical properties, cycloparaphenylenes (CPPs) are attractive building blocks for new materials synthesis. While both noncovalent interactions and irreversible covalent bonds have been used to link CPP monomers into extended materials, a coordination chemistry approach remains less explored. Here we show that nucleophilic aromatic substitution reactions can be leveraged to rapidly introduce donor groups (-OR, -SR) onto polyfluorinated CPP rings.

Geometry-dependent valence tautomerism, magnetism, and electrical conductivity in 1D iron-tetraoxolene chains.

Redox-active tetraoxolene ligands such as 1,4-dihydroxybenzoquinone provide access to a diversity of metal-organic architectures, many of which display interesting magnetic behavior and high electrical conductivity. Here, we take a closer look at how structure dictates physical properties in a series of 1D iron-tetraoxolene chains. Using a diphenyl-derivatized tetraoxolene ligand (HPhdhbq), we show that the steric profile of the coordinating solvent controls whether linear or helical chains are exclusively formed.

Oxidative control over the morphology of Cu(HHTP), a 2D conductive metal-organic framework.

The morphology of electrically conductive metal-organic frameworks strongly impacts their performance in applications such as energy storage and electrochemical sensing. However, identifying the appropriate conditions needed to achieve a specific nanocrystal size and shape can be a time-consuming, empirical process. Here we show how partial ligand oxidation dictates the morphology of Cu(HHTP) (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene), a prototypical 2D conductive metal-organic framework.