title: 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(mu-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, lambdamax = 492-533 nm; quantum yields, Phi = 0.6-0.8; and lifetimes, tau = 4.0-10.4 mus) at 298 K. In 2-methyltetrahydrofuran (2mTHF) solutions at 298 K, only 1 and 4 show weaker emission (Phi = 0.009) with shorter lifetimes (tau = 0.35 and 0.23 mus) and red-shifted spectra (lambdamax = 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 approximately 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 (Phi = 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 x 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/m(2), and maximum external quantum efficiency = 4.8%.
authors.affiliation: Leading-Edge Technology Development Headquarters, Canon Incorporated, Ohta-ku, Tokyo 146-8501, Japan. tsuboyama.akira@canon.co.jp
authors.forename: Akira
authors.initials: A
authors.lastname: Tsuboyama
authors.forename: Katsuaki
authors.initials: K
authors.lastname: Kuge
authors.forename: Manabu
authors.initials: M
authors.lastname: Furugori
authors.forename: Shinjiro
authors.initials: S
authors.lastname: Okada
authors.forename: Mikio
authors.initials: M
authors.lastname: Hoshino
authors.forename: Kazunori
authors.initials: K
authors.lastname: Ueno
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D002614:Chelating Agents / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006219:Halogens / Q000737:chemistry*; D049449:Luminescence; D009682:Magnetic Resonance Spectroscopy; D063065:Organophosphonates / Q000737:chemistry*
chemical_list: C519449:1,2-bis(diphenylphosphino)benzene; D001555:Benzene Derivatives; D002614:Chelating Agents; D006219:Halogens; D063065:Organophosphonates; D003300:Copper