Single-layer white polymer light-emitting diodes based on an iridium (III) complex containing alkyltrifluorene picolinic acid

To explore the relationship between the electronic properties of a host/dopant system and obtain a high-efficiency single-dopant white polymer light-emitting device two novel blue-emitting cyclometalated iridium (III) complexes of (dfppy)₂Ir(Tfl-pic) and (dfppy)₂Ir(Brfl-pic) have been synthesized and characterized, where dfppy is 2-(2,4-difluorophenyl)pyridine, Tfl-pic and Brfl-pic are picolinic acid derivatives containing trialkylfluorene and dibromoalkylfluorene units bridged with an alkoxy chain, respectively. Both iridium (III) complexes exhibited blue emission in dichloromethane solution and their neat films, and possessed good dispersibility and thermal properties. Two different devices using (dfppy)₂Ir(Tfl-pic) as a single component emitter and a blend of poly(N-vinylcarbazole) and 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole as the host matrix were fabricated. Improved white emission was obtained by adjusting the electron injection layer leading to efficient exciplex emission.     

Single-layer white polymer light-emitting diodes based on an iridium (III) complex containing alkyltrifluorene picolinic acid

To explore the relationship between the electronic properties of a host/dopant system and obtain a high-efficiency single-dopant white polymer light-emitting device two novel blue-emitting cyclometalated iridium (III) complexes of (dfppy)₂Ir(Tfl-pic) and (dfppy)₂Ir(Brfl-pic) have been synthesized and characterized, where dfppy is 2-(2,4-difluorophenyl)pyridine, Tfl-pic and Brfl-pic are picolinic acid derivatives containing trialkylfluorene and dibromoalkylfluorene units bridged with an alkoxy chain, respectively. Both iridium (III) complexes exhibited blue emission in dichloromethane solution and their neat films, and possessed good dispersibility and thermal properties. Two different devices using (dfppy)₂Ir(Tfl-pic) as a single component emitter and a blend of poly(N-vinylcarbazole) and 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole as the host matrix were fabricated. Improved white emission was obtained by adjusting the electron injection layer leading to efficient exciplex emission.     

Cyclometallated iridium(III) complexes with dicyanamide or tricyanomethanide

Reaction of cyclometallated iridium(III) complex Ir(ppy)₂(PPh₃)Cl (2, ppy = 2-phenylpyridine) with dicyanamide or tricyanomethanide gave neutral mononuclear complexes Ir(ppy)₂(PPh₃)N(CN)₂ (3a) or Ir(ppy)₂(PPh₃)C(CN)₃ (3b), and dicyanamide/tricyanomethanide-linked binuclear iridium(III) complexes [{Ir(ppy)₂(PPh₃)}₂N(CN)₂]⁺ (4a) or [{Ir(ppy)₂(PPh₃)}₂C(CN)₃]⁺ (4b). Substitution of coordinated chloride in the precursor 2 with dicyanamide or tricyanomethanide improved significantly the luminescence properties of 3a–4b. Compared with that in the precursor 2 (1.6%), 2.2 to 9.3-fold enhancement of emission quantum yields was detected in 3a–4b.     

Folic acid-modified iridium(III) coordination polymeric nanoparticles facilitating intracellular release of a phosphorescent residue capable of nuclear entry

Functional polymeric nanoparticles with folic acid end-capped poly(ethylene glycol) (PEG) as the shell and an iridium(III) complex coupled with poly(4-vinylpyridine) (P4VP)/[Ir(pq)₂] (pq = 2-phenylquinoline) as the core have been prepared through complexation of the pyridine moiety with [Ir(pq)₂]₂⁺ followed by dialysis against water. The nanoparticles with folic acid on the surface are capable of entering HeLa cells. It is significant that, after cellular internalization, the intracellular compound histidine can trigger release of the [Ir(pq)₂]⁺ residue into the nucleus from the nanoparticles. This provides a new pathway for triggering the release of drugs from their carriers.     

The Reaction of Tertiary Anilines with Maleimides under Visible Light Redox Catalysis

Tertiary anilines can be prompted to react with N‐aryl‐ and N‐benzylmaleimides to form tetrahydroquinoline products under photocatalysis using visible light irradiation, the ruthenium or iridium complexes Ru(bpy)₃Cl₂ or Ir(ppy)₂(dtbbpy)PF₆ as catalyst, and air as terminal oxidant.     

A site-isolated mononuclear iridium complex catalyst supported on MgO: Characterization by spectroscopy and aberration-corrected scanning transmission electron microscopy

Supported mononuclear iridium complexes with ethene ligands were prepared by the reaction of Ir(C₂H₄)₂(acac) (acac is CH₃COCHCOCH₃) with highly dehydroxylated MgO. Characterization of the supported species by extended X-ray absorption fine structure (EXAFS) and infrared (IR) spectroscopies showed that the resultant supported organometallic species were Ir(C₂H₄)₂, formed by the dissociation of the acac ligand from Ir(C₂H₄)₂(acac) and bonding of the Ir(C₂H₄)₂ species to the MgO surface. Direct evidence of the site-isolation of these mononuclear complexes was obtained by aberration-corrected scanning transmission electron microscopy (STEM); the images demonstrate the presence of the iridium complexes in the absence of any clusters. When the iridium complexes were probed with CO, the resulting IR spectra demonstrated the formation of Ir(CO)₂ complexes on the MgO surface. The breadth of the ν_CO bands demonstrates a substantial variation in the metal–support bonding, consistent with the heterogeneity of the MgO surface; the STEM images are not sufficient to characterize this heterogeneity. The supported iridium complexes catalyzed ethene hydrogenation at room temperature and atmospheric pressure in a flow reactor, and EXAFS spectra indicated that the mononuclear iridium species remained intact. STEM images of the used catalyst confirmed that almost all of the iridium complexes remained intact, but this method was sensitive enough to detect a small degree of aggregation of the iridium on the support.     

Electroluminescent Performances of Iridium Complexes with Dibenzo-18-crown-6

Three novel iridium complexes with dibenzo-18-crown-6 substituted 2-penylpyridine (ppy) ligand have been synthesized and characterized. In order to investigate the electroluminescent properties of the resulting iridium complexes, polymer light-emitting diodes (PLEDs) with device structure of ITO/PEDOT:PSS/Emissive Layer/LiF/Al are fabricated using soluble poly(N-vinylcarbazole) (PVK) as the host and the resultant iridium complexes as dopant. Consequently, the PLEDs with G1 as dopant exhibited the highest luminous efficiencies of 13.3 cd A^?1 and the maximal brightness of 13523 cd m^?2 at the doping concentration of 8 wt%. Moreover, the iridium complexes G1, G2 and G3 exhibited nearly identical Commission Internationale de L’Eclairage (CIE) coordinates of (0.34?±?0.1, 0.62?±?0.1), which are very close to the CIE coordinates of (0.33, 0.61) for Ir(ppy)₃. This indicates that the CIE coordinates of the iridium complexes would not be influenced as the dibenzo-18-crown-6 groups pended on the meta-position of benzene ring of ppy.     

Synthesis, crystal structure and photophysical properties of a series of new neutral iridium(III) complexes with 2-phenylpyridine

A series of new neutral iridium(III) complexes containing strong-field ancillary ligands, [Ir(ppy)₂(PPh₃)L] (ppy = 2-phenylpyridine, PPh₃ = triphenylphosphine, L = NCS⁻, 1; , 2; NCO⁻, 3), have been synthesized and fully characterized by ¹H NMR, IR, ESI mass spectral and elemental analysis. The crystal structure of 1 has been determined by X-ray analysis. The photoluminescence (PL) spectra of 1–3 show emission maxima at 477, 489 and 485 nm, respectively, corresponding to blue light-emitting of 1 and blue-green light-emitting of 2 and 3. PL quantum yields (PLQYs) of 1–3 are 0.39, 0.13 and 0.43, respectively.     

A cyclometalated iridium(III) complex that inhibits the migration and invasion of MDA-MB-231 cells

A cyclometalated iridium(III) complex, [Ir(ppy)₂(PCN)]Cl (Ir1, ppy = 2-phenylpyridine, PCN = 2-(4-cyanophenyl)imidazo[4,5-f] [1,10] phenanthroline), was synthesized and characterized in the present study. Ir1 inhibited the proliferation, migration and invasion of MDA-MB-231 human breast cancer cells in a dose-dependent manner. Moreover, Ir1 down-regulated the phosphorylation of AKT/ERK signal pathways. According to confocal fluorescence microscopy analysis, Ir1 was primarily localized within the mitochondria and induced apoptosis through an intrinsic mitochondria-mediated apoptotic pathway. Thus, Ir1 exhibited both antimetastatic and antineoplastic properties, indicating that Ir1 may be a viable drug candidate in antimetastasis and anticancer therapies.     

Enantioselective Synthesis of Chiral Tetrahydroisoquinolines by Iridium‐Catalyzed Asymmetric Hydrogenation of Enamines

Chiral iridium complexes based on spiro phosphoramidite ligands are demonstrated to be highly efficient catalysts for the asymmetric hydrogenation of unfunctionalized enamines with an exocyclic double bond. In combination with excess iodine or potassium iodide and under hydrogen pressure, the complex Ir/(S_a,R,R)‐ 3a provides chiral N‐alkyltetrahydroisoquinolines in high yields with up to 98% ee. The L/Ir ratio of 2:1 is crucial for obtaining a high reaction rate and enantioselectivity. A deuterium labeling experiment showed that an inverse isotope effect exists in this reaction. A possible catalytic cycle including an iridium(III) species bearing two monophosphoramidite ligands is also proposed.     

Electron-withdrawing groups and strong-field ligands containing iridium(III) complexes and their efficient blue light-emitting

Two new heteroleptic iridium(III) complexes [Ir(4,6-dfppy)₂(PPh₃)L] (4,6-dfppy = 2-(4,6-difluorophenyl)pyridyl, PPh₃ = triphenylphosphine, L = NCS^?, 1; NCO^?, 2) have been synthesized and fully characterized. By introduction of electron-withdrawing groups such as fluorine atoms on the 4- and 6-positions of 2-phenylpyridyl (ppy) and using strong-field ligands for instance PPh₃ and pseudohalogen as ancillary ligands, the HOMO–LUMO electronic energy gaps of 1 and 2 have been increased sufficiently. The photoluminescence (PL) spectra of 1 and 2 in solution show emission maxima at 456 and 458 nm, respectively, corresponding to efficient blue light-emitting. X-ray analyses show that intra- and intermolecular π–π interactions exist in the solid state of 1 and 2. The PL spectra of 1 and 2 in solid state exhibit about 30 nm spectral red shifts compared with those in solution.     

Aggregation-induced phosphorescence emission and pH recognition properties of an Iridium (III) complex

A novel Iridium (III) complex [Ir(ppy)₂(Hppip)]PF₆ (1) has been synthesized and characterized. The complex exhibits strong phosphorescence emission in high viscosity solvent glycerol and aggregation-induced phosphorescence emission in hexane solution. The high viscosity of glycerol and aggregation may restrict intramolecular rotation so that the compound exhibits stronger phosphorescence emission in glycerol and aggregated state. Compound 1 can also be a pH chemosensor to monitor pH changes in PBS buffer solution because of two successive protonation processes of pyridyl and imidazole moieties in acidic condition.     

Synthesis and X-ray crystal structure of a heteroleptic tris-cyclometalated iridium(III) complex

A convenient synthesis of the tris-cyclometalated complex [Ir(ppy)₂(nppy)] (2, ppy = 2-phenylpyridyl, nppy = 2-(4-nitrophenyl)pyridyl) from [{Ir(μ-Cl)(ppy)₂}₂] (1), the ligand 2-(4-nitrophenyl)pyridine, and silver trifluoroacetate as halide abstractor in refluxing methoxyethanol is described. The crystal and molecular structure of 2 was determined by a single-crystal X-ray diffraction study.     

Homogeneous Hydrogenation of Tri‐ and Tetrasubstituted Olefins: Comparison of Iridium‐Phospinooxazoline [Ir‐PHOX] Complexes and Crabtree Catalysts with Hexafluorophosphate (PF6) and Tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate (BArF) as Counterions

Four iridium complexes with achiral phosphino‐oxazoline (PHOX) ligands were readily prepared in two steps starting from commercially available phenyloxazolines. The air‐stable complexes with tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate (BAr_F) as counterion showed high reactivity in the hydrogenation of a range of tri‐ and tetrasubstituted olefins. The best results were obtained with an iridium complex ( 11 ) derived from a dicyclohexylphosphino‐oxazoline ligand bearing no additional substituents in the oxazoline ring. With several substrates, which gave only low conversion with the Crabtree catalyst, [Ir(Py)(PCy₃)(COD)]PF₆, full conversion was observed. The productivity of the Crabtree catalyst could be strongly increased by replacing the hexafluorophosphate anion with tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate. In one case, in the hydrogenation of a tetraalkyl‐substituted CC bond, [Ir(Py)(PCy₃)(COD)]BAr_F gave higher conversion than catalyst 11 . However, with several other substrates complex 11 proved to be superior.     

SIAPhos: Phosphorylated Sulfonimidamides and their Use in Iridium‐Catalyzed Asymmetric Hydrogenations of Sterically Hindered Cyclic Enamides

Phosphorylated sulfonimidamides (SIAPhos) undergo ion exchange reactions with cationic complexes, [Rh(cod)₂BF₄] and [Ir(cod)₂BarF], or neutral complexes [Rh(cod)Cl]₂ and [Ir(cod)Cl]₂, leading to unprecedented neutral complexes with P‐N‐S‐N chelates. Use of the resulting neutral iridium complexes in asymmetric hydrogenation reactions of tri‐ and tetrasubstituted enamides leads to products with high enantioselectivities (up to 92% ee).     

A convenient one-step synthesis of alkenyl-phosphonio complexes of ruthenium(II), rhodium(III) and iridium(III)

Alkenyl-phosphonio complexes of ruthenium(II), rhodium(III) and iridium(III) were prepared by reactions of [(p-cymene)RuCl₂(PPh₃)] or [C_p^*MCl₂(PPh₃)] (M=Rh, Ir; C_p^*=C₅Me₅) with 1-ethynylbenzene and triphenylphosphine in the presence of KPF₆.     

Novel yellow phosphorescent iridium complexes containing a carbazole–oxadiazole unit used in polymeric light-emitting diodes

Yellow iridium complexes Ir(PPOHC)₃ and (PPOHC)₂Ir(acac) (PPOHC: 3-(5-(4-(pyridin-2-yl)phenyl)-1,3,4-oxadiazol-2-yl)-9-hexyl-9H-carbazole) were synthesized and characterized. The Ir(PPOHC)₃ complex has good thermal stability with 5% weight-reduction occurring at 370 °C and a glass-transition temperature of 201 °C. A polymeric light-emitting diode using the Ir(PPOHC)₃ complex as a phosphorescent dopant showed a luminance efficiency of 16.4 cd/A and the maximum external quantum efficiency of 6.6% with CIE coordinates of (0.50, 0.49). A white polymeric light-emitting diode was fabricated using Ir(PPOHC)₃ which showed a luminance efficiency of 15.3 cd/A, with CIE coordinates of (0.39, 0.44). These results indicate that the iridium complexes containing a linked carbazole–oxadiazole unit are promising candidates in high-efficiency electroluminescent devices.     

Four new cyclometalated phenylisoquinoline-based Ir(III) complexes: Syntheses,structures, properties and DFT calculations

Four new cyclometalated phenylisoquinoline-based iridium(III) complexes [Ir(C^∧N)₂(bipy)]PF₆ (5a–5d) (bipy = 2,2′-bipyridine) have been synthesized and fully characterized, where the C^∧N ligands are 1-(4-(trifluoromethyl)phenyl)isoquinoline, 4-(isoquinolin-1-yl)benzaldehyde, 4-(isoquinolin-1-yl)benzonitrile and 1-(3-fluoro-4-methylphenyl)isoquinoline, respectively. The crystal structures of 5a and 5c have been determined. The photophysical and electrochemical properties of these new complexes 5a–5d have been studied. All Ir(III) complexes exhibit orange phosphorescence in dichloromethane solution at room temperature with a maximum at 593–618 nm, quantum yield of 0.046–0.16. The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 5a–5d have been calculated with density functional theory (DFT) and time-dependent DFT (TD-DFT).     

Graphene–NHC–iridium hybrid catalysts built through –OH covalent linkage

Graphene oxide (GO) and thermally reduced graphene oxide (TRGO) were covalently modified with imidazolium salts through their hydroxyl surface groups. The selective reaction of the –OH groups with p-nitrophenylchloroformate produced labile intermediate organic carbonate functions which were used for the covalent anchoring of a hydroxy-functionalized imidazolium salt. Nanohybrid materials containing iridium N-heterocyclic carbene (NHC)-type organometallic complexes were prepared by causing the imidazolium-functionalized materials to react with [Ir(μ-OMe)(cod)]₂. The iridium content of the graphene-based hybrid catalysts, as determined by XPS and ICP-MS was the order of ∼5 and 10 wt.%, for the TRGO and GO-based materials, respectively. The graphene-supported iridium hybrid materials were active in the heterogeneous hydrogen-transfer reduction of cyclohexanone to cyclohexanol with 2-propanol/KOH as the hydrogen source. The thermally reduced graphene–NHC–iridium hybrid catalyst showed the best catalytic performance with an initial TOF of 11.500 h⁻¹, slightly better than the related acetoxy-functionalized NHC iridium homogeneous catalyst. A good catalyst recyclability and stability were achieved.     

Household LED irradiation under air: cationic polymerization using iridium or ruthenium complex photocatalysts

Household LED bulbs are used to promote the ring-opening photopolymerization of epoxides in the presence of a photocatalyst (here tris(2-phenylpyridine)iridium [Ir(ppy)₃] or tris(1,10-phenanthroline)ruthenium(II) [Ru(phen)₃²⁺] complex) and a silyl radical source. Remarkably, even under this very soft irradiation (light intensity lower than 10 mW/cm2), excellent polymerization profiles are obtained i.e., this is the first reported use of such very convenient irradiation devices for photopolymerization processes. The role of the silane and other hydrogen donors is outlined.