Rational Design of Charge‐Neutral, Near‐Infrared‐Emitting Osmium(II) Complexes and OLED Fabrication

A new series of charge neutral Os(II) isoquinolyl triazolate complexes (1–4) with both trans and cis arrangement of phosphine donors are synthesized, and their structural, electrochemical and photophysical properties are established. In sharp contrast to the cis‐arranged complexes 2–4, the trans derivative 1, which shows a planar arrangement of chromophoric N‐substituted chelates, offers the most effective extended π‐delocalization and hence the lowest excited state energy gap. These complexes exhibit phosphorescence with peak wavelengths ranging from 692–805 nm in degassed CH2Cl2 at room temperature. Near‐infrared (NIR)‐emitting electroluminescent devices employing 6 wt % of 1 (or 4) doped in Alq3 host material are successfully fabricated. The devices incorporating 1 as NIR phosphor exhibit fairly intense emission with a peak wavelength at 814 nm. Forward radiant emittance reaches as high as 65.02 µW cm−2, and a peak EQE of ∼1.5% with devices employing Alq3, TPBi and/or TAZ as electron‐transporting/exciton‐blocking layers. Upon switching to phosphor 4, the electroluminescence blue shifts to 718 nm, while the maximum EQE and radiance increase to 2.7% and 93.26 (μW cm−2) respectively. Their performances are optimized upon using TAZ as the electron transporting and exciton‐blocking material. The OLEDs characterized represent the only NIR‐emitting devices fabricated using charge‐neutral and volatile Os(II) phosphors via thermal vacuum deposition.

[1]  Yun Chi,et al.  En Route to High External Quantum Efficiency (∼12%), Organic True‐Blue‐Light‐Emitting Diodes Employing Novel Design of Iridium (III) Phosphors , 2009 .

[2]  P. Chou,et al.  Blue to true-blue phosphorescent Ir(III) complexes bearing a nonconjugated ancillary phosphine chelate: strategic synthesis, photophysics, and device integration. , 2009, ACS applied materials & interfaces.

[3]  K. Schanze,et al.  Near infrared organic light-emitting devices based on donor-acceptor-donor oligomers , 2008 .

[4]  Shizuo Tokito,et al.  Highly efficient, deep-blue phosphorescent organic light emitting diodes with a double-emitting layer structure , 2008 .

[5]  Gang Qian,et al.  Band Gap Tunable, Donor−Acceptor−Donor Charge-Transfer Heteroquinoid-Based Chromophores: Near Infrared Photoluminescence and Electroluminescence , 2008 .

[6]  Yun Chi,et al.  Highly efficient blue-emitting iridium(III) carbene complexes and phosphorescent OLEDs. , 2008, Angewandte Chemie.

[7]  V. Roy,et al.  Deep-red to near-infrared electrophosphorescence based on bis(8-hydroxyquinolato) platinum(II) complexes , 2008 .

[8]  J. Kalinowski,et al.  Excimer-based red/near-infrared organic light-emitting diodes with very high quantum efficiency , 2008 .

[9]  C. Shu,et al.  Luminescent osmium(II) complexes with functionalized 2-phenylpyridine chelating ligands: preparation, structural analyses, and photophysical properties. , 2008, Inorganic chemistry.

[10]  Ho Jung Chang,et al.  Triplet host engineering for triplet exciton management in phosphorescent organic light-emitting diodes , 2008 .

[11]  Karsten Walzer,et al.  Near-infrared organic light emitting diodes based on heavy metal phthalocyanines , 2008 .

[12]  C. Shu,et al.  Strategic design and synthesis of osmium(II) complexes bearing a single pyridyl azolate pi-chromophore: achieving high-efficiency blue phosphorescence by localized excitation. , 2007, Inorganic chemistry.

[13]  Yun Chi,et al.  Contemporary progresses on neutral, highly emissive Os(II) and Ru(II) complexes. , 2007, Chemical Society reviews.

[14]  Julie J. Brown,et al.  Photophysics of Pt-porphyrin electrophosphorescent devices emitting in the near infrared , 2007 .

[15]  Yun Chi,et al.  Blue-emitting heteroleptic iridium(III) complexes suitable for high-efficiency phosphorescent OLEDs. , 2007, Angewandte Chemie.

[16]  Stephen R Forrest,et al.  Highly efficient, near-infrared electrophosphorescence from a Pt-metalloporphyrin complex. , 2007, Angewandte Chemie.

[17]  Hasuck Kim,et al.  Efficient Electrogenerated Chemiluminescence from Bis-Cyclometalated Iridium(III) Complexes with Substituted 2-Phenylquinoline Ligands , 2007 .

[18]  J. Kalinowski,et al.  Highly efficient near-infrared organic excimer electrophosphorescent diodes , 2007 .

[19]  Yun Chi,et al.  Phosphorescent dyes for organic light-emitting diodes. , 2007, Chemistry.

[20]  Min Xu,et al.  Red to near-infrared electrophosphorescence from a platinum complex coordinated with 8-hydroxyquinoline , 2006 .

[21]  C. Shu,et al.  A new family of homoleptic Ir(III) complexes: tris-pyridyl azolate derivatives with dual phosphorescence. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[22]  Z. Wang,et al.  Near-Infrared Electrochromic and Electroluminescent Polymers Containing Pendant Ruthenium Complex Groups , 2006 .

[23]  Yun Chi,et al.  Osmium‐ and Ruthenium‐Based Phosphorescent Materials: Design, Photophysics, and Utilization in OLED Fabrication , 2006 .

[24]  Jian Li,et al.  Organic light-emitting diodes having exclusive near-infrared electrophosphorescence , 2006 .

[25]  Yun Chi,et al.  Orange and Red Organic Light‐Emitting Devices Employing Neutral Ru(II) Emitters: Rational Design and Prospects for Color Tuning , 2006 .

[26]  P. Douglas,et al.  Coordination complexes exhibiting room-temperature phosphorescence: Evaluation of their suitability as triplet emitters in organic light emitting diodes , 2006 .

[27]  Ken-Tsung Wong,et al.  Highly Efficient Organic Blue Electrophosphorescent Devices Based on 3,6‐Bis(triphenylsilyl)carbazole as the Host Material , 2006 .

[28]  F. Loiseau,et al.  Bridging ligand planarity as a route to long-lived, near infrared emitting dinuclear ruthenium(II) complexes. , 2006, Chemical communications.

[29]  Ken‐Tsung Wong,et al.  Employing ambipolar oligofluorene as the charge-generation layer in time-of-flight mobility measurements of organic thin films , 2006 .

[30]  P. Chou,et al.  Room-temperature NIR phosphorescence of new iridium (III) complexes with ligands derived from benzoquinoxaline , 2006 .

[31]  J. Bünzli,et al.  Taking advantage of luminescent lanthanide ions. , 2005, Chemical Society reviews.

[32]  Shizuo Tokito,et al.  Phosphorescent-sensitized triplet-triplet annihilation in tris(8-hydroxyquinoline) aluminum , 2005 .

[33]  P. Borowicz,et al.  Electrochemiluminescence studies of the cyclometalated iridium(III) L2Ir(acetyl acetonate) complexes , 2005 .

[34]  Ulrich S. Schubert,et al.  New Trends in the Use of Transition Metal–Ligand Complexes for Applications in Electroluminescent Devices , 2005 .

[35]  Yun Chi,et al.  Organic Light‐Emitting Diodes based on Charge‐Neutral RuII Phosphorescent Emitters , 2005 .

[36]  Jinhua Yang,et al.  Synthesis and Near IR Photoluminescence of Os(II) Bis(2,2′- Bipyridine) (3,8-diarylethynyl-1,10-phenanthroline) Complexes: Anomalous Behavior in the 3,8-dinitrophenylethynyl-substituted Homologue , 2005 .

[37]  P. Chou,et al.  Organic light-emitting diodes based on charge-neutral Os(II) emitters: generation of saturated red emission with very high external quantum efficiency , 2005 .

[38]  Jan Birnstock,et al.  High-efficiency and low-voltage p‐i‐n electrophosphorescent organic light-emitting diodes with double-emission layers , 2004 .

[39]  P. Chou,et al.  Solvent-Polarity Tuning Excited-State Charge Coupled Proton-Transfer Reaction in p-N,N-Ditolylaminosalicylaldehydes , 2004 .

[40]  Ye Tao,et al.  Highly Efficient Red Phosphorescent Osmium(II) Complexes for OLED Applications , 2004 .

[41]  P. Chou,et al.  Synthesis and characterization of luminescent osmium(II) carbonyl complexes based on chelating dibenzoylmethanate and halide ligands. , 2003, Chemical communications.

[42]  R. Humphry-Baker,et al.  Highly phosphorescence iridium complexes and their application in organic light-emitting devices. , 2003, Journal of the American Chemical Society.

[43]  J. Salbeck,et al.  Organic Materials for Photonic Devices , 2003 .

[44]  J. W. Hofstraat,et al.  Electroluminescent device with reversible switching between red and green emission , 2003, Nature.

[45]  Serge I. Gorelsky,et al.  Electronic structure and spectra of ruthenium diimine complexes by density functional theory and INDO/S. Comparison of the two methods , 2001 .

[46]  D. Zou,et al.  Carrier Mobilities in Organic Electron Transport Materials Determined from Space Charge Limited Current , 2001 .

[47]  Stephen R. Forrest,et al.  Transient analysis of organic electrophosphorescence. II. Transient analysis of triplet-triplet annihilation , 2000 .

[48]  D. Gamelin,et al.  Design of luminescent inorganic materials: new photophysical processes studied by optical spectroscopy. , 2000, Accounts of chemical research.

[49]  G. Scuseria,et al.  An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules , 1998 .

[50]  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 .

[51]  S. Forrest,et al.  Highly efficient phosphorescent emission from organic electroluminescent devices , 1998, Nature.

[52]  M. Kappes,et al.  Experiment versus Time Dependent Density Functional Theory Prediction of Fullerene Electronic Absorption , 1998 .

[53]  Dennis R. Salahub,et al.  Dynamic polarizabilities and excitation spectra from a molecular implementation of time‐dependent density‐functional response theory: N2 as a case study , 1996 .

[54]  Gross,et al.  Excitation energies from time-dependent density-functional theory. , 1996, Physical review letters.

[55]  M. Sinclair,et al.  Electron and hole mobility in tris(8‐hydroxyquinolinolato‐N1,O8) aluminum , 1995 .

[56]  A. Becke Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[57]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[58]  H. Bouchriha,et al.  Triplet exciton — trapped hole interaction in anthracene crystals , 1971 .

[59]  R. Kepler,et al.  TRIPLET EXCITONS AND DELAYED FLUORESCENCE IN ANTHRACENE CRYSTALS , 1963 .

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

[61]  J. G. Haasnoot,et al.  Synthesis, spectroscopic, and electrochemical properties of bis(2,2′-bipyridyl)-ruthenium compounds of some pyridyl-1,2,4-triazoles , 1987 .

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

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

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

[65]  P. C. Hariharan,et al.  Accuracy of AH n equilibrium geometries by single determinant molecular orbital theory , 1974 .