E-type delayed fluorescence of a phosphine-supported Cu2(mu-NAr2)2 diamond core: harvesting singlet and triplet excitons in OLEDs.

A highly emissive bis(phosphine)diarylamido dinuclear copper(I) complex (quantum yield = 57%) was shown to exhibit E-type delayed fluorescence by variable temperature emission spectroscopy and photoluminescence decay measurement of doped vapor-deposited films. The lowest energy singlet and triplet excited states were assigned as charge transfer states on the basis of theoretical calculations and the small observed S(1)-T(1) energy gap. Vapor-deposited OLEDs doped with the complex in the emissive layer gave a maximum external quantum efficiency of 16.1%, demonstrating that triplet excitons can be harvested very efficiently through the delayed fluorescence channel. The function of the emissive dopant in OLEDs was further probed by several physical methods, including electrically detected EPR, cyclic voltammetry, and photoluminescence in the presence of applied current.

[1]  David J. Giesen,et al.  The MIDI! basis set for quantum mechanical calculations of molecular geometries and partial charges , 1996 .

[2]  W. R. Wadt,et al.  Ab initio effective core potentials for molecular calculations , 1984 .

[3]  A. Listorti,et al.  Novel phenanthroline ligands and their kinetically locked copper(I) complexes with unexpected photophysical properties. , 2006, Inorganic chemistry.

[4]  D Murphy,et al.  Highly phosphorescent bis-cyclometalated iridium complexes: synthesis, photophysical characterization, and use in organic light emitting diodes. , 2001, Journal of the American Chemical Society.

[5]  F. Lytle,et al.  Simultaneous emissions including intraligand emission and charge-transfer emission from [bis(triphenylphosphine)(phenanthroline)copper](1+) , 1979 .

[6]  Bin Li,et al.  Realization of High-Energy Emission from [Cu(N−N)(P−P)]+ Complexes for Organic Light-Emitting Diode Applications , 2009 .

[7]  P. C. Ford,et al.  Photophysical studies in solution of the tetranuclear copper(I) clusters Cu4I4L4 (L = pyridine or substituted pyridine) , 1991 .

[8]  Qisheng Zhang,et al.  Novel Heteroleptic CuI Complexes with Tunable Emission Color for Efficient Phosphorescent Light‐Emitting Diodes , 2007 .

[9]  D. McMillin,et al.  Simple Cu(I) complexes with unprecedented excited-state lifetimes. , 2002, Journal of the American Chemical Society.

[10]  M. Frisch,et al.  Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields , 1994 .

[11]  Vivian Wing-Wah Yam,et al.  Design of luminescent polynuclear copper(I) and silver(I) complexes with chalcogenides and acetylides as the bridging ligands , 1998 .

[12]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[13]  D. Giesen,et al.  Charge carriers and triplets in OLED devices studied by electrically detected electron paramagnetic resonance , 2009 .

[14]  Sergey Lamansky,et al.  Synthesis and characterization of phosphorescent cyclometalated platinum complexes. , 2001, Inorganic chemistry.

[15]  Peter C. Ford,et al.  Photochemical and photophysical studies of tetranuclear copper(I) halide clusters: an overview , 1994 .

[16]  N. Armaroli,et al.  Highly luminescent Cu(I)-phenanthroline complexes in rigid matrix and temperature dependence of the photophysical properties. , 2001, Journal of the American Chemical Society.

[17]  J. Deaton,et al.  Narrow-line and broadband spectra of iridium(III) complexes in a Shpol'skii matrix and an amorphous host. , 2006, The journal of physical chemistry. A.

[18]  Ching Wan Tang,et al.  Nonradiative recombination centers and electrical aging of organic light-emitting diodes: Direct connection between accumulation of trapped charge and luminance loss , 2003 .

[19]  C. Tang,et al.  Organic Electroluminescent Diodes , 1987 .

[20]  D. McMillin,et al.  Hindered internal conversion in rigid media. Thermally nonequilibrated 3IL and 3CT emissions from [Cu(5-X-phen)(PPh3)2]+ and [Cu(4,7-X2-phen)(PPh3)2]+ systems in a glass at 77 K , 1987 .

[21]  Junji Kido,et al.  Ultra High Efficiency Green Organic Light-Emitting Devices , 2006 .

[22]  D. McMillin,et al.  Luminescence of some CuI complexes , 1982 .

[23]  Jillian L Dempsey,et al.  Long-lived and efficient emission from mononuclear amidophosphine complexes of copper. , 2007, Inorganic chemistry.

[24]  Hartmut Yersin,et al.  Low-Lying Electronic States and Photophysical Properties of Organometallic Pd(II) and Pt(II) Compounds. Modern Research Trends Presented in Detailed Case Studies , 2001 .

[25]  A. Listorti,et al.  Photochemistry and Photophysics of Coordination Compounds: Copper , 2007 .

[26]  W. R. Wadt,et al.  Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi , 1985 .

[27]  J. Peters,et al.  A highly emissive Cu2N2 diamond core complex supported by a [PNP]- ligand. , 2005, Journal of the American Chemical Society.

[28]  W. R. Wadt,et al.  Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals , 1985 .

[29]  Herbert H. H. Homeier,et al.  Triplet sublevels of metal organic complexes – temperature dependence of spin–lattice relaxation , 2000 .

[30]  M. Knudsen,et al.  Die Molekularströmung der Gase durch Offnungen und die Effusion , 1909 .

[31]  Koichi Nozaki,et al.  Structure-dependent photophysical properties of singlet and triplet metal-to-ligand charge transfer states in copper(I) bis(diimine) compounds. , 2003, Inorganic chemistry.

[32]  Dennis R. Salahub,et al.  Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold , 1998 .

[33]  Johann Strasser,et al.  Triplets in metal–organic compounds. Chemical tunability of relaxation dynamics , 2000 .

[34]  M. Vitale,et al.  Photoluminescence properties of the structurally analogous tetranuclear copper(I) clusters Cu4X4(dpmp)4 (X = I, Br, Cl; dpmp = 2-(diphenylmethyl)pyridine) , 1993 .

[35]  X. Jing,et al.  Highly Efficient Electroluminescence from Green‐Light‐Emitting Electrochemical Cells Based on CuI Complexes , 2006 .

[36]  J. Deaton,et al.  The blue aluminum and gallium chelates for OLEDs , 2008 .

[37]  Walter J. Finkenzeller,et al.  Emission of Ir(ppy)3. Temperature dependence, decay dynamics, and magnetic field properties , 2003 .

[38]  C. H. Chen,et al.  Electroluminescence of doped organic thin films , 1989 .

[39]  S. Forrest,et al.  Nearly 100% internal phosphorescence efficiency in an organic light emitting device , 2001 .

[40]  J. D. Shore,et al.  Highly efficient fluorescent-phosphorescent triplet-harvesting hybrid organic light-emitting diodes , 2010 .

[41]  Junji Kido,et al.  High Luminous Efficiency Blue Organic Light-Emitting Devices Using High Triplet Excited Energy Materials , 2007 .

[42]  Qisheng Zhang,et al.  Highly Efficient Green Phosphorescent Organic Light‐Emitting Diodes Based on CuI Complexes , 2004 .

[43]  Hartmut Yersin,et al.  Triplet emitters for OLED applications. Mechanisms of exciton trapping and control of emission properties , 2004 .

[44]  Peter C. Ford,et al.  Photoluminescence Properties of Multinuclear Copper(I) Compounds. , 1999, Chemical reviews.

[45]  R. Ahlrichs,et al.  Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory , 1996 .

[46]  Akira Tsuboyama,et al.  Photophysical properties of highly luminescent copper(I) halide complexes chelated with 1,2-bis(diphenylphosphino)benzene. , 2007, Inorganic chemistry.

[47]  D. McMillin,et al.  Steric Effects in the Ground and Excited States of Cu(NN)2+ Systems , 1997 .

[48]  T. Meyer Photochemistry of metal coordination complexes: metal to ligand charge transfer excited states , 1986 .

[49]  Bin Li,et al.  High light electroluminescence of novel Cu(I) complexes , 2009 .

[50]  Donal D. C. Bradley,et al.  Angular Dependence of the Emission from a Conjugated Polymer Light‐Emitting Diode: Implications for efficiency calculations , 1994 .

[51]  S. Forrest,et al.  VERY HIGH-EFFICIENCY GREEN ORGANIC LIGHT-EMITTING DEVICES BASED ON ELECTROPHOSPHORESCENCE , 1999 .

[52]  P. Gantzel,et al.  A HIGHLY EMISSIVE HETEROLEPTIC COPPER(I) BIS(PHENANTHROLINE) COMPLEX : CU(DBP)(DMP)+ (DBP = 2,9-DI-TERT-BUTYL-1,10-PHENANTHROLINE; DMP = 2,9-DIMETHYL- 1,10-PHENANTHROLINE) , 1999 .

[53]  D. Kondakov Role of triplet‐triplet annihilation in highly efficient fluorescent devices , 2009 .

[54]  M. G. Mason,et al.  Anode modification in organic light-emitting diodes by low-frequency plasma polymerization of CHF3 , 2001 .

[55]  Paul E. Burrows,et al.  Organic Light-Emitting Devices for Solid-State Lighting , 2008 .

[56]  D. McMillin,et al.  Synthesis and structural characterization of Cu(I) and Ni(II) complexes that contain the bis[2-(diphenylphosphino)phenyl]ether ligand. Novel emission properties for the Cu(I) species. , 2002, Inorganic chemistry.

[57]  Roland E. Gamache,et al.  Temperature dependence of luminescence from Cu(NN)2+ systems in fluid solution. Evidence for the participation of two excited states , 1983 .

[58]  Alexander J. M. Miller,et al.  Probing the electronic structures of [Cu2(mu-XR2)]n+ diamond cores as a function of the bridging X atom (X = N or P) and charge (n = 0, 1, 2). , 2008, Journal of the American Chemical Society.