Synthesis, mesomorphism, photophysics and device performance of liquid-crystalline pincer complexes of gold(iii)

Emissive gold(iii) complexes of pincer 2,6-diphenylpyridines also bearing a phenylacetylide ligand have been modified at both the pincer and phenylacetylide to confer liquid crystalline properties, with most complexes showing a columnar hexagonal phase in the condensed phase. Solution NMR studies show a preferred orientation for self-association, consistent with structural parameters in the liquid crystal phase obtained by X-ray methods. While the pattern of substitution of the phenylacetylide has no discernible effect on the photophysics, when two alkoxy chains are attached to the pincer ligands, photoluminescence quantum yields (PLQY) of around 3% are found, whereas when four alkoxy chains are attached the PLQY increases significantly to 36%. Insight from computational chemistry indicated that the incorporation of the alkoxy donor groups raises the energy of the pincer-based HOMO−1 orbital, with a concomitant lowering of the LUMO ← HOMO−1 transition energy, consistent with an experimentally observed red shift. The gold complexes were fabricated into OLED devices using solution processing methods, being doped into the emissive layer at 5%, leading to external quantum efficiencies of up to 7.14%, values that compare well with those of related complexes in the literature.