Ligand-controlled and nanoconfinement-boosted luminescence employing Pt(ii) and Pd(ii) complexes: from color-tunable aggregation-enhanced dual emitters towards self-referenced oxygen reporters

In this work, we describe the synthesis, structural and photophysical characterization of four novel Pd(ii) and Pt(ii) complexes bearing tetradentate luminophoric ligands with high photoluminescence quantum yields (phi(L)) and long excited state lifetimes (tau) at room temperature, where the results were interpreted by means of DFT calculations. Incorporation of fluorine atoms into the tetradentate ligand favors aggregation and thereby, a shortened average distance between the metal centers, which provides accessibility to metal-metal-to-ligand charge-transfer ((MMLCT)-M-3) excimers acting as red-shifted energy traps if compared with the monomeric entities. This supramolecular approach provides an elegant way to enable room-temperature phosphorescence from Pd(ii) complexes, which are otherwise quenched by a thermal population of dissociative states due to a lower ligand field splitting. Encapsulation of these complexes in 100 nm-sized aminated polystyrene nanoparticles enables concentration-controlled aggregation-enhanced dual emission. This phenomenon facilitates the tunability of the absorption and emission colors while providing a rigidified environment supporting an enhanced phi(L) up to about 80% and extended tau exceeding 100 mu s. Additionally, these nanoarrays constitute rare examples for self-referenced oxygen reporters, since the phosphorescence of the aggregates is insensitive to external influences, whereas the monomeric species drop in luminescence lifetime and intensity with increasing triplet molecular dioxygen concentrations (diffusion-controlled quenching).

Automated summary

This work presents the synthesis, structural, and photophysical characteristics of novel Pd(II) and Pt(II) complexes with high photoluminescence quantum yields and long excited state lifetimes. DFT calculations were used to interpret the results, showing the impact of incorporating fluorine atoms into the ligands and the achievement of room-temperature phosphorescence through a supramolecular approach. Encapsulation of the complexes in nanoparticles enables concentration-controlled aggregation-enhanced dual emission, supporting enhanced photoluminescence quantum yields up to 80% and extended excited state lifetimes exceeding 100 μs.