Yansong
Feng
a,
Xuming
Zhuang
a,
Dongxia
Zhu
b,
Yu
Liu
*a,
Yue
Wang
a and
Martin R.
Bryce
*c
aState Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China. E-mail: yuliu@jlu.edu.cn
bInstitute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Renmin Road 5268, Changchun, Jilin 130024, P. R. China
cDepartment of Chemistry, Durham University, Durham DH1 3LE, UK. E-mail: m.r.bryce@durham.ac.uk
First published on 19th October 2016
Two new deep-blue iridium(III) complexes, (dfpypy)2IrFptz (Ir1) and (Medfpypy)2IrFptz (Ir2), comprising difluoro-bipyridyl (dfpypy) derivatives as cyclometaling ligands and a chelated pyridyl-triazole (Fptz) ancillary ligand are reported. The bipyridyl ligands lead to a significantly increased HOMO–LUMO gap and a hypsochromic shift of the phosphorescence compared to phenylpyridyl analogs. Density function theory (DFT) calculations and electrochemical measurements for Ir1 and Ir2 support their genuine blue phosphorescent emission. The combination of ancillary and cyclometalating ligands in Ir1 and Ir2 significantly influences the molecular orbitals of both complexes, leading to clearly distinct electron density distributions of the HOMO and LUMO compared with other blue-emitting Ir(III) derivatives. Both complexes Ir1 and Ir2 show deep-blue emission with λmax values in the region of 435–465 nm with high PLQYs and short excited-state lifetimes. The phosphorescent organic light emitting diodes (PhOLEDs) based on Ir1 and Ir2 achieve remarkably high EL performance with low efficiency roll-off at high luminance. The bluest color (CIEx,y 0.14, 0.11) and the highest EL efficiency were achieved in the device based on Ir2 (Device 2), where the peak EQE/PE of 13.0%/11.2 lm W−1 together with the corresponding values of 12.6%/8.8 lm W−1 and 10.1%/5.0 lm W−1 at the practical luminances of 100 and 1000 cd m−2 respectively, strongly compete with those of any deep-blue fluorescent and/or phosphorescent OLEDs with similar CIE coordinates previously reported.
Chou et al. prepared two iridium complexes using pyridyl azolates and benzyl phenylphosphine ligands,7 which are among the most efficient true-blue PhOLEDs documented to date with CIEx,y of ∼(0.15, 0.11) and the peak EQEs/PEs (power efficiencies) of ∼11%/8 lm W−1, respectively. Nevertheless, they exhibited relatively high turn-on voltages of ≥4.4 V as well as significant efficiency roll-off (∼8% and 3 lm W−1 at the practical luminance of 100 cd m−2). Forrest and coworkers have very recently reported that PhOLEDs of an Ir complex of N-heterocyclic carbene ligands can attain EQEmax of 10.1 ± 0.2% at very low luminance and EQE 9.0 ± 0.1% at 1000 cd m−2 with CIEx,y 0.16, 0.09.8 Thus, it remains very important to develop blue phosphors for realizing very efficient deep-blue PhOLEDs that meet the requirements for practical applications.
Generally, the effective molecular design concept for deep-blue phosphors is to introduce electron-withdrawing or electron-donating groups at selective positions on the cyclometalated (C^N) ligands. For example, fluorine substitution leads to the 4′,6′-difluorophenylpyridinato ligand in the well-known sky-blue iridium complex FIrpic,2b,3a,c,9 resulting in a larger band gap and blue shifted emission.10 Alternatively, fluorine-substituted 2,3′-bipyridine derivatives, where the additional nitrogen atom has a similar or even stronger effect of lowering the HOMO (highest occupied molecular orbital) level (as opposed to introducing the electron-withdrawing groups at the para position on the phenyl ring),11 have shown potential as the cyclometalating ligands for efficient deep-blue iridium complexes. It is also well known that the blue color can be tuned through structural variations of the ancillary ligand.12 For example, chelated pyridyl-triazole derivatives, which usually give very low total synthesis yields of ≤10% for the resulting complexes, afford stable iridium complexes that show remarkably shorter emission maxima than that of FIrpic, due to their blue-shifting effect compared to picolinate and other ancillary liands.4c,5b,10a,11c,12b
The aim of the present work was to develop new phosphors and to fabricate deep-blue PhOLEDs with enhanced efficiency. To achieve this, we designed and characterized two new heteroleptic Ir(III) complexes (Ir1 and Ir2) containing the unique combination of 2′,6′-difluoro-2,3′-bipyridyl ligands (dfpypy or Medfpypy) and a 5-(2′-pyridyl)-3-trifluoromethyl-1,2,4-triazole ancillary ligand (Fptz). We demonstrate that both Ir1 and Ir2 display true-blue phosphorescence in their solution and film states, and they serve in the emitting layer (EML) of PhOLEDs that show deep-blue emission with very high EL efficiencies. The Ir2-based device (Device 2) represents the deepest blue emission with CIEx,y of (0.14, 0.11) near to the ideal value of (0.14, 0.08). The peak EQE/PE values are 13%/11.2 lm W−1, which maintain very high levels of 12.6%/8.8 lm W−1 and 10.1%/5.0 lm W−1 at luminances of 100 and 1000 cd m−2, respectively. To the best of our knowledge, these EL efficiency values strongly compete with, and even exceed, those previously reported for PhOLEDs with similar CIE coordinates.5–7,13a Additionally, an effective synthetic route for Fptz13b,c provides high yields of Ir1 and Ir2 (>70%), facilitating the low cost of both complexes in the quest for deep-blue PhOLEDs in the future.
The molecular structures of Ir1 and Ir2 in single crystals were determined by X-ray diffraction. As shown in Fig. 1a and Table S1 in the ESI,† both complexes exhibit distorted octahedral geometries around the iridium center with the classical C,C-cis and N,N-trans configurations. The bond lengths and angles are summarized in Table S2 (ESI†). The Ir–C bond lengths, ranging from 1.981 to 2.008 Å, and Ir–N (in dfpypy) bond lengths, ranging from 2.040 to 2.055 Å, are comparable to those observed in several blue-emitting Ir(III) complexes (Ir–C = 1.997–2.005 Å for Ir(dfpypy)3; Ir–C = 1.992–2.009 Å for Ir(dfpypy)2(pic); Ir–C = 2.009–2.013 Å for Ir(dfpypy)2(fppz); Ir–N = 2.116–2.136 Å for Ir(dfpypy)2(pic); Ir–N = 2.044–2.048 Å for Ir(dfpypy)2(fppz)).11
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Fig. 1 (a) ORTEP plots of the X-ray molecular structures of Ir1 and Ir2. Hydrogen atoms are omitted for clarity. (b and c) Molecular orbital diagrams for Ir1/Ir2 and two reference complexes (RIr1/RIr2) with selected isodensity frontier molecular orbitals mainly involved in the electronic transitions. All the DFT energy values are given in electron volts (eV). The structures of RIr1 and RIr2 are shown in Fig. S3 (ESI†). |
Density functional theory (DFT) calculations were performed in order to estimate the energy levels and electron density distributions of the orbitals of Ir1 and Ir2 together with two reported reference complexes RIr1 and RIr2,11c,12b which have two difluorophenylpyridinato-N,C2 main ligands (dfppy and Medfppy) instead of dfpypy and Medfpypy, respectively (see Fig. S3 in ESI†). Fig. 1b and c show the optimized structures and a schematic representation of the energy levels of the four complexes. The HOMOs of RIr1 and RIr2 are mostly localized on both dfppy ligands together with the iridium atom, whereas the HOMOs of Ir1 and Ir2 are distributed over one of the two dfpypy ligands and the metal d orbitals, also with a significant contribution from the ancillary ligand orbital. This clear difference results in much lower HOMO levels of Ir1 and Ir2 (−6.29 and −6.19 eV, respectively) compared to RIr1 and RIr2 (−5.73 and −5.63 eV, respectively). On the other hand, the LUMOs are distributed similarly in all four complexes over part of one of the main ligands as well as the ancillary ligand. Thus, although Ir1 and Ir2 show lower LUMO levels of −2.10 and −1.99 eV compared to RIr1 and RIr2 (−1.79 and −1.72 eV) respectively, the difference of the LUMO energy between Ir1 and Ir2 and the corresponding reference complexes is lower than for the HOMO. These data lead to the larger HOMO–LUMO energy gaps of ∼4.2 eV for Ir1 and Ir2, compared to ∼3.9 eV for RIr1 and RIr2. These data confirm that the bipyridyl cyclometalating ligand of Ir1 and Ir2 is beneficial for achieving the desired blue shift in the phosphorescent emission compared to the phenylpyridyl analogs. The improvement in the purity of blue emission from Ir1 and Ir2 is experimentally confirmed by the photophysical and electrochemical studies described below.
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Fig. 2 UV-vis absorption and PL spectra in CH2Cl2 at room temperature (a) and PL spectra in THF at low temperature (77 K) (b) of Ir1 and Ir2. PL spectra (c) and luminescence decay profiles (d) of tBu-CPO films doped with 10 wt% Ir1 and Ir2. Emission data were obtained in degassed solutions. The structure of tBu-CPO is shown in Fig. S3 (ESI†). |
Both Ir1 and Ir2 show similar intense blue phosphorescence in solution (RT) with emission at λmax 437, 466 nm (RT)/438, 468 nm (77 K) for Ir1 and 435, 464 nm (RT)/437, 467 nm (77 K) for Ir2 (Fig. 2b), which are strongly blue shifted compared to RIr1 and RIr2 (∼460, 490 nm)11c,12b in agreement with the DFT calculations above. The photoluminescence (PL) emission and the transient PL properties of thin films using t-BuCPO15 as host doped with complexes of Ir1 and Ir2 (10 wt%) were measured. Both films displayed strong and structured phosphorescence spectra with similar emission maxima in the deep blue 430–470 nm region (Fig. 2c) to those in solution. The PL quantum yields (PLQYs) were 0.65 ± 0.03 and 0.70 ± 0.03, by employing an integrating sphere. The excited-state lifetimes of Ir1 and Ir2 are monoexponential and are 2.97 μs and 3.01 μs, respectively, consistent with their emission originating from a triplet excited state. The PL spectra and transient PL of the doped films are shown in Fig. 2c and d.
The solution electrochemical properties of Ir1 and Ir2 were investigated by cyclic voltammetry (CV), and both complexes exhibit reversible reduction and oxidation behaviour as shown in Fig. S6 (ESI†). The respective HOMO and LUMO energy levels were experimentally determined from the redox curves relative to the vacuum level, and are −6.27 and −2.57 eV for Ir1, −6.24 and −2.56 eV for Ir2. These data show that Ir1 and Ir2 have larger HOMO–LUMO gaps than RIr1 and RIr2 with the HOMO/LUMO values of ∼−5.6/−2.9 eV.11c Therefore, the electrochemical, photophysical and computational data are entirely consistent and demonstrate that the novel combination of main and ancillary ligands in Ir1 and Ir2, where cyclometalating C^N bipyridine ligands are employed instead of phenylpyridine ligands, leads to a distinctively different HOMO/LUMO distribution compared to previous blue-emitting Ir(III) complexes10,11 and explains the observed deep blue emission.
The devices showed stable EL spectra (Fig. 3b) within a range of driving voltages (4–8 V) (Fig. S8, ESI†), and no host emission is observed in the EL spectra, which also exhibit good color durability after continuous open-condition operation for 2 hours. Deep-blue EL with two λELmax bands at 430–440 nm and 460–470 nm at a current density of 5 mA cm−2 (∼500 cd m−2) resemble the PL spectra of the complexes. Owing to the blue-region emitting peaks of both devices, together with their full width at half maximum (FWHM) of less than 50 nm, the similar CIE coordinates of (0.15, 0.13) and (0.14, 0.11) were obtained. Fig. 3b shows a photograph of Device 2 demonstrating the observed color purity. It is interesting to note that the relative intensities at the shortest wavelength bands of Ir1 and Ir2 are higher in the EL than in the PL spectra due to optical microcavity effects,16 leading to the desired deep-blue EL. The current density–voltage–luminance (J–V–L) and EL efficiency–luminance (PE/EQE–L) characteristics are shown in Fig. 3c and d, respectively, and the EL data are summarized in Table 1. Devices 1 and 2 exhibit rather low turn-on voltages of ∼3.5 V, indicating also that these HTL–EML–ETL systems possess the predominant factor facilitating both hole and electron injection and transport,8,17 which also dominated the rapidly increasing J–V and L–V curves after the onset, where the driving voltages are as low as 5.0/4.7 V and 7.3/6.4 V at the practical luminances of 100 and 1000 cd m−2, respectively. Furthermore, the peak EQEs/PEs of 11.2%/11.1 lm W−1 and 13.0%/11.2 lm W−1 with remarkably low roll-off were obtained in Devices 1 and 2, respectively. Device 2 shows the bluest color and the higher EQE/PE in terms not only of the peak values above, but also by maintaining such high levels as 12.6%/8.8 lm W−1 and 10.1%/5.0 lm W−1 at the luminances of 100 and 1000 cd m−2, respectively, which are needed for practical displays and/or solid-state lighting. Here, the slight improved EL performance of Ir2 compared to Ir1 indicates that the methyl substituent could partly suppress the aggregation of the emitting core in the solid thin films, and thereby favour enhanced device EL efficiency.18 To the best of our knowledge, these EL efficiencies strongly compete with, and even exceed, any previously reported values for deep-blue PhOLEDs with similar CIEx,y values.5–8
V on [V] | L max [cd m−2] | η ext [%] | η p [lm W−1] | CIE(x,y)c | |
---|---|---|---|---|---|
a Applied voltage required to reach a luminance of 1 cd m−2. b The efficiencies listed are the maximum values, and the values at 100 and 1000 cd m−2, respectively. c Recorded at 1000 cd m−2. | |||||
1 | 3.5 | 5080 | 11.2, 10.8, 8.3 | 11.1, 7.9, 4.2 | 0.15, 0.13 |
2 | 3.5 | 4710 | 13.0, 12.6, 10.1 | 11.2, 8.8, 5.0 | 0.14, 0.11 |
For comparison, we note that deep-blue OLEDs using a thermally-activated delayed fluorescence (TADF) organic (metal-free) emitter achieve 20% EQE at 100 cd m−2 with roll-off to ca. 12% at 1000 cd m−2.19 However, the TADF-OLEDs' CIEx,y coordinates (0.15, 0.13) are less blue than our Device 2, and the complicated TADF device architecture with seven separate organic layers could limit practical applications.
Footnote |
† Electronic supplementary information (ESI) available: Synthesis and characterization details; differential scanning calorimetric (DSC) and thermogravimetric analysis (TGA) data; X-ray crystallographic data files (CIF), crystal data and structure refinement parameters; cyclic voltammograms for Ir1 and Ir2. CCDC 1052634 and 1052689. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6tc04119a |
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