Pyridylarsine-based Cu(i) complexes showing TADF mixed with fast phosphorescence: a speeding-up emission rate using arsine ligands

Can arsine ligands be preferred over similar phosphines to design Cu(I)-based TADF materials? The present study reveals that arsines can indeed be superior to reach shorter decay times of Cu(I) emitters. This has been exemplified on a series of bis(2-pyridyl)phenylarsine-based complexes [Cu₂(Py₂AsPh)₂X₂] (X = Cl, Br, and I), the emission decay times of which are significantly shorter (2-9 μs at 300 K) than those of their phosphine analogs [Cu₂(Py₂PPh)₂X₂] (5-33 μs). This effect is caused by two factors: (i) large ΔE(S₁-T₁) gaps of the arsine complexes (1100-1345 cm^-1), thereby phosphorescence is admixed with TADF at 300 K, thus reducing the total emission decay time compared to the TADF-only process by 5-28%; (ii) higher SOC strength of arsenic (ζ_l = 1202 cm^-1) against phosphorus (ζ_l = 230 cm^-1) makes the k_r(T₁ → S₀) rate of the Cu(I)-arsine complexes by 1.3 to 4.2 times faster than that of their phosphine analogs. It is also noteworthy that the TADF/phosphorescence ratio for [Cu₂(Py₂AsPh)₂X₂] at 300 K is halogen-regulated and varies in the order: Cl (1 : 1) < Br (3 : 1) ≈ I (3.5 : 1). These findings provide a new insight into the future design of dual-mode (TADF + phosphorescence) emissive materials with reduced lifetimes.