Cyclo‑<i>meta</i>‑phenylene Revisited: Nickel-Mediated Synthesis, Molecular Structures, and Device Applications

From a one-pot nickel-mediated Yamamoto-type coupling reaction of m-dibromobenzene, five congeners of [n]­cyclo-meta-phenylenes were synthesized and fully characterized. The [n]­cyclo-meta-phenylenes possessed a commonly shared arylene unit and intermolecular contacts but varied in packing structures in the crystalline solid state. Columnar assembly of larger congeners yielded nanoporous crystals with carbonaceous walls to capture minor protic or aliphatic solvent molecules. The concise and scalable synthesis allowed exploration of the macrocyclic hydrocarbons as bipolar charge carrier transport materials in organic light-emitting diode devices.