Phosphorescent Platinum(II) Complexes with a Spiro-fused Xanthene Unit: Synthesis and Photophysical Properties.

Novel platinum(II) complexes, derived from the spiro[fluorene-9,9'-xanthene] (SFX) motif, were synthesized and combined with different auxiliary ligands such as acetylacetonate (acac), bis(2,4,6-trimethylphenyl)propane-1,3-dionate (mesacac) and dihydrobis(3,5-dimethylpyrazole-1-yl) borate. The final products were obtained in yields of up to 36 % and characterized by NMR, X-ray and combustion analysis. These complexes have structured green-blue emission spectra with Commission Internationale de l'Éclairage (CIExy ) coordinates of (0.21;0.46). Excellent photoluminescence quantum yields (PLQYs) ranging from 87 %-91 % were found. The emission lifetimes vary from 33 μs to 43 μs. Calculations on the B3LYP/6-311++G** level of theory reveal, that the nature of the emissive state is dependent on the positional regioisomerism of the SFX motif. The 2-SFX complexes demonstrate ligand-centered (3 LC) emission, while the 2'-SFX regioisomer with the mesacac ligand shows a strong 3 MLCT character.