Azaacene containing iridium(III) phosphors: elaboration of the π-conjugation effect and application in highly efficient solution-processed near-infrared OLEDs.

Azaacenes have attracted wide research interest due to their tremendous potential in organic electronics. However, near-infrared (NIR) light-emitting iridium(III) phosphors bearing azaacene derivatives are rarely investigated. In this contribution, two solution-processable heteroleptic iridium(III) complexes, namely DBPzIr and PPzIr, are rationally designed and synthesized, and they contain a rigid phenanthrene- or pyrene-fused diazaacene core and two peripheral groups of 4-tert-butyl-phenyl attached at the 12,13-positions in the core, respectively. The effects of the diazaacene core and appending groups on the optoelectronic properties of both complexes are systematically investigated. A dramatically red-shifted NIR emission peak at 789 nm with a photoluminescence quantum yield (PLQY) of 14% is observed in PPzIr compared with the 746 nm emission with a PLQY of 40% in DBPzIr. Taking advantage of their photophysical properties, the solution-processed device doped with DBPzIr achieves a maximum external quantum efficiency (EQEmax) of 8.00% with a radiance of 54 866 mW Sr-1 m-2 at 716 nm and the device doped with PPzIr exhibits a significantly red-shifted emission at 772 nm with an EQEmax of 3.53%. The achieved device performance is among the best values in the reported NIR-OLEDs based on iridium(III) complexes via a solution process at the same color gamut. Our study indicates that the reasonable collocation of the rigid diazaacene chelating core and flexible peripheral groups in the iridium(III) complex is of great significance in designing highly efficient NIR emitters.

Engineering of Cyano Functionalized Benzo[d]imidazol-2-ylidene Ir(III) Phosphors for Blue Organic Light-Emitting Diodes.

In this study, we designed and synthesized three series of blue emitting homoleptic iridium(III) phosphors bearing 4-cyano-3-methyl-1-phenyl-6-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (mfcp), 5-cyano-1-methyl-3-phenyl-6-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (ofcp), and 1-(3-(tert-butyl)phenyl)-6-cyano-3-methyl-4-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (5-mfcp) cyclometalates, respectively. These iridium complexes exhibit intense phosphorescence in the high energy region of 435-513 nm in the solution state at RT, to which the relatively large T1 → S0 transition dipole moment is beneficial for serving as a pure emitter and an energy donor to the multiresonance thermally activated delayed fluorescence (MR-TADF) terminal emitters via Förster resonance energy transfer (FRET). The resulting OLEDs achieved true blue, narrow bandwidth EL with a max EQE of 16-19% and great suppression of efficiency roll-off with ν-DABNA and t-DABNA. We obtained the FRET efficiency up to 85% using titled Ir(III) phosphors f-Ir(mfcp)3 and f-Ir(5-mfcp)3 to achieve true blue narrow bandwidth emission. Importantly, we also provide analysis on the kinetic parameters involved in the energy transfer processes and, accordingly, propose feasible ways to improve the efficiency roll-off caused by the shortened radiative lifetime of hyperphosphorescence.

Blue Phosphorescence and Hyperluminescence Generated from Imidazo[4,5-b]pyridin-2-ylidene-Based Iridium(III) Phosphors.

Four isomeric, homoleptic iridium(III) metal complexes bearing 5-(trifluoromethyl)imidazo[4,5-b]pyridin-2-ylidene and 6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-ylidene-based cyclometalating chelates are successfully synthesized. The meridional isomers can be converted to facial isomers through acid induced isomerization. The m-isomers display a relatively broadened and red-shifted emission, while f-isomers exhibit narrowed blue emission band, together with higher photoluminescent quantum yields and reduced radiative lifetime relative to the mer-counterparts. Maximum external quantum efficiencies of 13.5% and 22.8% are achieved for the electrophosphorescent devices based on f-tpb1 and m-tpb1 as dopant emitter together with CIE coordinates of (0.15, 0.23) and (0.22, 0.45), respectively. By using f-tpb1 as the sensitizing phosphor and t-DABNA as thermally activated delayed fluorescence (TADF) terminal emitter, hyperluminescent OLEDs are successfully fabricated, giving high efficiency of 29.6%, full width at half maximum (FWHM) of 30 nm, and CIE coordinates of (0.13, 0.11), confirming the efficient Förster resonance energy transfer (FRET) process.

Homoleptic Ir(III) Phosphors with 2-Phenyl-1,2,4-triazol-3-ylidene Chelates for Efficient Blue Organic Light-Emitting Diodes.

In this report, we synthesized two series of deep-blue-emitting homoleptic iridium(III) phosphors bearing 1,2,4-triazol-3-ylidene and 5-(trifluoromethyl)-1,2,4-triazol-3-ylidene cyclometalate. Compared with reported synthetic routes using Ag2O as the promoter, herein, we adopted a different strategy to furnish these complexes in high yields. Also, the meridional to facial isomerization was executed in the presence of trifluoroacetic acid. These phosphors were examined using NMR spectroscopies, single-crystal X-ray diffraction studies, and photophysical methods. The results revealed that electron-withdrawing trifluoromethyl substitution on the N-heterocyclic carbene fragment only gave a minor variation of photoluminescence peak wavelengths and a decrease in radiative lifetime but notable reduction in thermal stabilities. The parent 1,2,4-triazol-3-ylidene complexes have been demonstrated to be suitable for use as deep-blue phosphors, with structured emission with the peak max. located at ∼420 nm and with photoluminescence quantum yields in a range of 34.8-42.5% in degassed THF solution at RT. Fabrication of both the phosphorescent organic light-emitting diodes (OLEDs) and phosphor-sensitized OLEDs (or hyperphosphorescence) was successfully conducted, from which the OLED device based on m-tz1 showed a max. external quantum efficiency (EQE) of 10% with CIEx,y coordinates of 0.15, 0.06, while the corresponding hyperphosphorescent OLED using m-tz2 as a sensitizer and t-DABNA as a terminal emitter afforded a significantly improved max. EQE of 19.7%, EL λmax of 468 nm, and FWHM of 31 nm with CIEx,y coordinates of 0.12, 0.13.

Rational Tuning of Bis-Tridentate Ir(III) Phosphors to Deep-Blue with High Efficiency and Sub-microsecond Lifetime.

A new class of bis-tridentate Ir(III) complexes (Dap-1-4) was synthesized using carbene pincer pro-chelates PC1·H3(PF6)2 or PC2·H3(PF6)2 with either imidazolylidene or imidazo[4,5-b]pyridin-2-ylidene appendages, together with a second cyclometalating 2,6-diaryoxypyridine chelate, L1H2 and L2H2, differed by a NMe2 donor at the central pyridinyl fragment. The respective emission tuning between the ultraviolet and blue region was rationalized using time-dependent density functional theory (TD-DFT) approaches. Next, a highly efficient blue emitter (Dap-5) was synthesized by concomitant addition of two methyl groups and a single CF3 substituent at the central phenyl and peripheral imidazo[4,5-b]pyridin-2-ylidene entities of the carbene pincer chelate, respectively. The organic light-emitting diode (OLED) device with 15 wt % Dap-5 in DPEPO shows electroluminescence at 468 nm and with CIE (0.14, 0.15) and a max external quantum efficiency (max EQE) of 16.8% with low efficiency roll-off (EQE of 14.4% at 1000 cd m-2); the latter is attributed to the relatively shortened triplet excited-state radiative lifetime. These results highlight the adequateness of bis-tridentate Ir(III) phosphors in fabrication of practical blue-emitting OLEDs.

Achieving near-infrared emission in platinum(II) complexes by using an extended donor-acceptor-type ligand.

A series of C^N ligands with donor-acceptor (D-A) frameworks, i.e. TPA-BTPy, TPA-BTPy-Fl and Fl(TPA-BTPy)2, as well as their mono- and di-nuclear platinum(II) complexes of (TPA-BTPy)Pt(pic), (TPA-BTPy-Fl)Pt(pic) and [Fl(TPA-BTPy)2]Pt2(pic)2 are respectively designed and synthesized, in which triphenylamine (TPA) and fluorene (Fl) are used as the D units, 4-(pyrid-2-yl)benzothiadiazole (BTPy) as the A unit, and the picolinate anion (pic) as the auxiliary ligand. Their thermal, photophysical and electrochemical characteristics were investigated. Compared to mono-nuclear platinum complexes and their free ligands, this dinuclear one of [Fl(TPA-BTPy)2]Pt2(pic)2 shows an obvious interaction from the platinum atom to ligand and dual emission peaks at 828 and 601 nm in thin films. Upon oxidation with antimony pentachloride in dichloromethane, charge transfer transitions between the platinum and ligand are observed for the three complexes. The single-emissive-layer polymer light-emitting devices doped with [Fl(TPA-BTPy)2]Pt2(pic)2 display a strong electroluminescence with dual emission peaks at 780 and 600 nm at a dopant concentration over 4 wt%. A maximum external quantum efficiency of 0.02% with a radiance of 59 µW cm(-2) is obtained in the device at 30 wt% dopant concentration. This work indicates that the use of an extended D-A-type ligand is an effective strategy to achieve NIR emission for platinum complexes in PLEDs.