Photophysical Properties of Highly Luminescent Copper(I) Halide Complexes Chelated with 1,2-Bis(diphenylphosphino)benzene

Abstract

Studies on synthesis, structures, and photophysics have been carried out for a series of luminescent copper(I) halide complexes with the chelating ligand, 1,2-bis[diphenylphosphino]benzene (dppb). The complexes studied are halogen-bridged dinuclear complexes, [Cu(μ-X)dppb]₂ (X = I (1), Br (2), Cl (3)), and a mononuclear complex, CuI(dppb)(PPh₃) (4). These complexes in the solid state exhibit intense blue-green photoluminescence with microsecond lifetimes (emission peaks, λ_max = 492−533 nm; quantum yields, Φ = 0.6−0.8; and lifetimes, τ = 4.0−10.4 μs) at 298 K. In 2-methyltetrahydrofuran (2mTHF) solutions at 298 K, only 1 and 4 show weaker emission (Φ = 0.009) with shorter lifetimes (τ = 0.35 and 0.23 μs) and red-shifted spectra (λ_max = 543 and 546 nm). The emission in the solid state originates from the (M + X)LCT excited state with a distorted-tetrahedral conformation, in which emissive excited states, ¹(M + X)LCT and ³(M + X)LCT, are in equilibrium with an energy difference of ∼2 kcal/mol. On the other hand, the complexes in the 2mTHF solutions emit from the MLCT excited state with an energetically favorable flattened conformation in the temperature range of 298−130 K. The flattened geometry with equilibrated ¹MLCT and ³MLCT states has a nonradiative rate at least 2 orders of magnitude larger than that of the distorted-tetrahedral geometry, leading to a much smaller emission quantum yield (Φ = 0.009) at 298 K. Since the flattening motion is markedly suppressed below 130 K, the emission observed in 2mTHF below 130 K is considered to occur principally from the (M + X)LCT state with a distorted-tetrahedral geometry. To interpret the photophysics of 1 and 4 in both the solid and solution states, we have proposed the “2-conformations with 2-spin-states model (2C × 2S model)”. The electroluminescence device using (1) as a green emissive dopant showed a moderate EL efficiency; luminous efficiency = 10.4 cd/A, power efficiency = 4.2 lm/W at 93 cd/m², and maximum external quantum efficiency = 4.8%.