A Concise Synthetic Strategy for Accessing Ambient Stable Bisphenalenyls toward Achieving Electroactive Open-Shell π-Conjugated Materials.

Open-shell, π-conjugated molecules represent exciting next-generation materials due to their unique optoelectronic and magnetic properties and their potential to exploit unpaired spin densities to engineer exceptionally close π-π interactions. However, prior syntheses of ambient stable, open-shell molecules required lengthy routes and displayed intermolecular spin-spin coupling with limited dimensionality. Here we report a general fragment-coupling strategy with phenalenone that enables the rapid construction of both biradicaloid (Ph2- s-IDPL, 1) and radical [10(OTf)] bisphenalenyls in ≤7 steps from commercial starting materials. Significantly, we have discovered an electronically stabilized π-radical cation [10(OTf)] that shows multiple intermolecular closer-than-vdW contacts (<3.4 Å) in its X-ray crystal structure. DFT simulations reveal that each of these close π-π interactions allows for intermolecular spin-spin coupling to occur and suggests that 10(OTf) achieves electrostatically enhanced intermolecular covalent-bonding interactions in two dimensions. Single crystal devices were fabricated from 10(OTf) and demonstrate average electrical conductivities of 1.31 × 10-2 S/cm. Overall, these studies highlight the practical synthesis and device application of a new π-conjugated material, based on a design principle that promises to facilitate spin and charge transport.

Methanol-Assisted ADMET Polymerization of Semiaromatic Amides.

A method for the acyclic diene metathesis polymerization of semiaromatic amides is described. The procedure uses second-generation Grubbs' catalyst and N-cyclohexyl-2-pyrrolidone (CHP), a high boiling, polar solvent capable of solubilizing both monomer and polymer. The addition of methanol to the reaction was found to significantly increase polymer molar mass although the role of the alcohol is currently not understood. Hydrogenation with hydrogen gas and Wilkinson's catalyst resulted in near-quantitative saturation. All polymers synthesized here exhibit a hierarchical semicrystalline morphology driven by ordering of aromatic amide groups via strong nonbonded interactions. Furthermore, the melting points can be tuned over a >100 °C range by precise substitution at just one of the backbone positions on each mer (<5% of the total).