Enhanced luminescence properties through heavy ancillary ligands in [Pt(C^N^C)(L)] complexes, L = AsPh₃ and SbPh₃

In the frame of our research aiming to develop efficient triplet-emitting materials, we are exploring the concept of introducing additional heavy atoms into cyclometalated transition metal complexes to enhance intersystem-crossing (ISC) and thus triplet emission through increased spin-orbit coupling (SOC). In an in-depth proof-of-principle study we investigated the double cyclometalated Pt(II) complexes [Pt(C^N^C)(PnPh₃)] (HC^N^CH = 2,6-diphenyl-pyridine (H₂dpp) or dibenzoacridine (H₂dba); Pn = pnictogen atoms P, As, Sb, or Bi) through a combined experimental and theoretical approach. The derivatives containing Pn = P, As, and Sb were synthesised and characterised comprehensively using single crystal X-ray diffraction (scXRD), UV-vis absorption and emission spectroscopy, transient absorption (TA) spectroscopy and cyclic voltammetry (CV). Across the series P < As < Sb, a red-shift is observed concerning absorption and emission maxima as well as optical and electrochemical HOMO-LUMO gaps. Increased photoluminescence quantum yields Φ_L and radiative rates k_r from mixed metal-to-ligand charge transfer (MLCT)/ligand centred (LC) triplet states are observed for the heavier homologues. Transient absorption spectroscopy showed processes in the ps range that were assigned to the population of the T₁ state by ISC. The heavy PnPh₃ ancillary ligands are found to enhance the emission efficiency due to both higher Pt-Pn bond strength and stronger SOC related to increased MLCT character of the excited states. The experimental findings are mirrored in hybrid (TD-)DFT calculations. This allowed for extrapolation to the rather elusive Bi derivatives, which were synthetically not accessible. This shortcoming is attributed to the transmetalation of phenyl groups from BiPh₃ to Pt, as supported by experimental NMR/MS as well as DFT studies.