Synthesis and metalation of polycatechol nanohoops derived from fluorocycloparaphenylenes
Ashlyn A. Kamin, Tara D. Clayton, Claire E. Otteson, Paige M. Gannon, Sebastian M. Krajewski, Werner Kaminsky, Ramesh Jasti, Dianne J. Xiao
Abstract
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. Demethylation of methoxide-substituted CPPs produces polycatechol nanohoop ligands that are readily metalated to produce well-defined, multimetallic CPP complexes. As catechols are recurring motifs throughout coordination chemistry and dynamic covalent chemistry, the polycatechol nanohoops reported here open the door to new strategies for the bottom-up synthesis of atomically precise CPP-based materials.