Tuning State Energies for Narrow Blue Emission in Tetradentate Pyridyl-Carbazole Platinum Complexes.

Narrow, deep blue emitters are highly desired in the field of organic light emitting diodes for high quality full color display and solid-state lighting applications. PtNON is reported as a deep blue emitting phosphor but is limited by its broad emission spectrum, making it unsuitable for high quality full color display applications. In this work, we report a strategy to fine-tune the color and the emission line shape of PtNON derivatives by incorporating electron donating (methyl or methoxy) or withdrawing (trifluoromethyl) substituent groups at the positions para to the nitrogen of the pyridines in PtNON. These substitutions resulted in destabilization or stabilization of the charge transfer state (CT) relative to the ligand centered (LC) state, resulting in complexes with narrow or broad emission spectra in various media. PtNON-OMe emits predominantly from the LC state, giving a narrow emission spectrum with fwhm = 48 nm in any media. PtNON-Me emits largely from the LC state in nonpolar media (fwhm = 54 nm) and predominantly from the CT state in polar media (fwhm = 83 nm). Last, PtNON-CF3 emits solely from the CT state in any media, giving it a broad emission spectrum (fwhm = 98 nm). The photoluminescence quantum yields of PtNON-OMe, PtNON-Me, and PtNON-CF3 in 1% doped PMMA films are 89, 95 and 20% with emission lifetimes of 27.1, 7.17, and 0.96 μs, respectively.

[1]  R. Haiges,et al.  "Quick-Silver" from a Systematic Study of Highly Luminescent, Two-Coordinate, d10 Coinage Metal Complexes. , 2019, Journal of the American Chemical Society.

[2]  S. Forrest,et al.  Highly Efficient Photo- and Electroluminescence from Two-Coordinate Cu(I) Complexes Featuring Nonconventional N-Heterocyclic Carbenes. , 2019, Journal of the American Chemical Society.

[3]  R. Haiges,et al.  Eliminating nonradiative decay in Cu(I) emitters: >99% quantum efficiency and microsecond lifetime , 2019, Science.

[4]  Wei Huang,et al.  Probing Triplet Excited States and Managing Blue Light Emission of Neutral Tetradentate Platinum(II) Complexes. , 2018, The journal of physical chemistry letters.

[5]  Yafei Luo,et al.  Theoretical insight into the photodeactivation pathway of the tetradentate Pt(II) complex: The π‐conjugation effect , 2018 .

[6]  G. Cheng,et al.  Highly Luminescent Pincer Gold(III) Aryl Emitters: Thermally Activated Delayed Fluorescence and Solution-Processed OLEDs. , 2017, Angewandte Chemie.

[7]  Jian Li,et al.  CuCl-Catalyzed Hydroxylation of N-Heteroarylcarbazole Bromide: Approach for the Preparation of N-Heteroarylcarbazolyl Phenols and Its Application in the Synthesis of Phosphorescent Emitters. , 2017, The Journal of organic chemistry.

[8]  Jian Li,et al.  Modifying Emission Spectral Bandwidth of Phosphorescent Platinum(II) Complexes Through Synthetic Control. , 2017, Inorganic chemistry.

[9]  Johannes M. Richter,et al.  Research data supporting "High-performance light-emitting diodes based on carbene-metal-amides" , 2017 .

[10]  Tyler B Fleetham,et al.  Phosphorescent Pt(II) and Pd(II) Complexes for Efficient, High‐Color‐Quality, and Stable OLEDs , 2017, Advanced materials.

[11]  Yuanbin She,et al.  CuCl-Catalyzed Ullmann-Type C-N Cross-Coupling Reaction of Carbazoles and 2-Bromopyridine Derivatives. , 2017, The Journal of organic chemistry.

[12]  J. Sworakowski,et al.  On the reliability of determination of energies of HOMO and LUMO levels in organic semiconductors from electrochemical measurements. A simple picture based on the electrostatic model , 2016 .

[13]  Tyler B Fleetham,et al.  Tetradentate Pt(II) Complexes with 6-Membered Chelate Rings: A New Route for Stable and Efficient Blue Organic Light Emitting Diodes , 2016 .

[14]  Tyler B Fleetham,et al.  Highly Efficient and Stable Narrow‐Band Phosphorescent Emitters for OLED Applications , 2015 .

[15]  Yi-Chun Wong,et al.  Bipolar gold(III) complexes for solution-processable organic light-emitting devices with a small efficiency roll-off. , 2014, Journal of the American Chemical Society.

[16]  Tyler B Fleetham,et al.  Efficient “Pure” Blue OLEDs Employing Tetradentate Pt Complexes with a Narrow Spectral Bandwidth , 2014, Advanced materials.

[17]  Stephen R Forrest,et al.  Tenfold increase in the lifetime of blue phosphorescent organic light-emitting diodes , 2014, Nature Communications.

[18]  Jianqiang Wang,et al.  Simple and High Efficiency Phosphorescence Organic Light-Emitting Diodes with Codeposited Copper(I) Emitter , 2014 .

[19]  C. Che,et al.  Strongly phosphorescent palladium(II) complexes of tetradentate ligands with mixed oxygen, carbon, and nitrogen donor atoms: photophysics, photochemistry, and applications. , 2013, Angewandte Chemie.

[20]  Jian Li,et al.  Highly efficient blue-emitting cyclometalated platinum(II) complexes by judicious molecular design. , 2013, Angewandte Chemie.

[21]  N. Bakken,et al.  Cyclometalated platinum complexes with luminescent quantum yields approaching 100%. , 2013, Inorganic chemistry.

[22]  C. Adachi,et al.  Highly efficient organic light-emitting diodes from delayed fluorescence , 2012, Nature.

[23]  V. Fattori,et al.  Blue-shifting the monomer and excimer phosphorescence of tridentate cyclometallated platinum(II) complexes for optimal white-light OLEDs. , 2012, Chemical communications.

[24]  Andreas F. Rausch,et al.  The triplet state of organo-transition metal compounds. Triplet harvesting and singlet harvesting for efficient OLEDs , 2011 .

[25]  Chunmiao Han,et al.  A simple phosphine-oxide host with a multi-insulating structure: high triplet energy level for efficient blue electrophosphorescence. , 2011, Chemistry.

[26]  Bo Qu,et al.  Recent Progresses on Materials for Electrophosphorescent Organic Light‐Emitting Devices , 2011, Advanced materials.

[27]  H. Loebl,et al.  Fluorine cleavage of the light blue heteroleptic triplet emitter FIrpic , 2009 .

[28]  Evan L. Williams,et al.  Excimer‐Based White Phosphorescent Organic Light‐Emitting Diodes with Nearly 100 % Internal Quantum Efficiency , 2007 .

[29]  H. Kwok,et al.  A novel class of phosphorescent gold(III) alkynyl-based organic light-emitting devices with tunable colour. , 2005, Chemical communications.

[30]  Stephen R. Forrest,et al.  The path to ubiquitous and low-cost organic electronic appliances on plastic , 2004, Nature.

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

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

[33]  Jacopo Tomasi,et al.  A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics , 1997 .