Bis-cyclometalated Iridium Research Articles

PVP formulations of bis-cyclometalated iridium(III) complexes bearing β-modified porphyrin ligands: characterization and photodynamic action on bladder cancer cells

PVP formulations of bis-cyclometalated iridium(III) complexes bearing β-modified porphyrin ligands: characterization and photodynamic action on bladder cancer cells

Suppression of efficiency roll-off in solution-processed OLEDs using pyrimidine-based iridium complexes modified with sterically hindered groups

Three bis-cyclometalated iridium complexes Ir1-Ir3 were successfully synthesized through mild reaction conditions. All complexes exhibit emission peaks at 507-509 nm, with excellent photoluminescence quantum efficiencies (PLQY) ranging from 69% to 97%. Self-quenching is significantly reduced because the steric spacers lead to minimum bimolecular interactions. Accordingly, the electroluminescence device based on complex Ir3 exhibits a maximum luminous efficiency of 39.6 cd A−1, a high EQE of 13.1% with an efficiency roll-off of 4.2% at 1000 cd m−2, which is much smaller than that (10.8%) of the Ir1-based device. Moreover, its devices exhibit excellent stability even at elevated doping concentrations, suggesting a notable reduction in intermolecular interactions caused by the steric pinene spacer.

Dual-emitting cyclometalated Ir(III) complexes with salicylaldimine-bound fluorophores for ratiometric oxygen sensing.

A new class of oxygen-sensing dual-emitting cyclometalated Ir(III) complexes is described. They function as ratiometric sensors that combine the blue fluorescence from coumarin as a self-referenced internal standard with yellow to red phosphorescence from bis-cyclometalated iridium complexes. The compounds have phosphorescence quantum yields up to 15%, lifetimes ranging from 0.23 to 9.4 μs, and are capable of sensing a wide range of O2 partial pressures.

Tunability of triplet excited states and photophysical behaviour of bis-cyclometalated iridium(III) complexes with imidazo[4,5-f][1,10]phenanthroline.

This is a comprehensive study of the photophysical behaviour of heteroleptic iridium(III) complexes with imidazo[4,5-f][1,10]phenanthroline (imphen) as an ancillary ligand, represented by the general formula [Ir(N∩C)2(imphen)]PF6. As cyclometalating ligands, 2-phenylpyridine (Hppy), 2-phenylquinoline (Hpquin), 2-phenylbenzothiazole (Hpbztz), and 2-(2-pyridyl)benzothiophene (pybzthH) were used. The impact of structural modifications of cyclometalating ligands was widely explored by a combination of steady-state and time-resolved optical techniques accompanied by theoretical calculations. We evidenced that the cyclometalating ligands induce essential changes in the nature of the emissive excited state and the emission characteristics of [Ir(N∩C)2(imphen)]PF6. While the complex [Ir(ppy)2(imphen)]PF6 (1) is a typical 3MLLCT emitter, the lowest triplet states of [Ir(pquin)2(imphen)]PF6 (2), [Ir(pbztz)2(imphen)]PF6 (3) and [Ir(pybzth)2(imphen)]PF6 (4) have a predominant 3LCN∩C character. The phosphorescence colour of the investigated Ir(III) complexes changes from greenish-yellow to red, their quantum yields vary from 56 to 2%, and their triplet excited-state lifetimes fall in the 743-3840 ns range. The highest photoluminescence quantum yield was revealed for 2 in CH2Cl2, while complex 3 in MeCN shows the most pronounced increase in the lifetime. Both complexes 2 and 3 show an increased efficiency of singlet oxygen generation. The herein discussed structure-property relationships are of high significance for controlling photoinduced processes in heteroleptic iridium(III) complexes with the imphen-based ancillary ligand, and making further progress in effectively tuning the emission energies, quantum yields and excited-state lifetimes of these systems by structural modifications of cyclometalating ligands, especially the π-conjugation, the position of the N-donor and the presence of sulfur heteroatoms.

Bis-oxazoline derivatives as ancillary ligands for bis-cyclometalated iridium complexes

Organometallic iridium complexes with two cyclometalated ligands (C^N) and one bis-oxazoline derived ancillary ligand (L^X), i.e. (C^N)2Ir(L^X), are reported. The C^N ligands are 1-phenylpyrazoline (ppz), 2-(4,6-difluorophenyl)pyridine (F2ppy), 2-phenylpyridine (ppy), 1-phenylisoquinoline (piq). The box ligand is (4S-+)-phenyl-α-[(4S)-phenyloxazolidin-2-ylidene]-2-oxazoline-2-acetonitrile. The emission of these complexes span across the visible and into the near-ultraviolet region of the electromagnetic spectrum with moderate to high photoluminescence quantum yields (ΦPL = 0.45–1.0). These complexes were found to emit from a metal-ligand to ligand charge transfer (ML'LCT) state and have lifetimes (1.3–2.1 μs), radiative rates (105 s−1), and nonradiative rates (104–105 s−1) comparable to state-of-the-art iridium emitters. The (ppy)2Ir(BOX-CN) complexes were resolved into the Δ- and Λ- diastereomers using differences in their solubility and additionally characterized by x-ray crystallography, stability, and chiroptic studies. The high ΦPL of these isomers results in the best to date brightness for circularly polarized luminescence (CPL) from iridium complexes (7.0 M−1 cm−1), with dissymmetry factors of −0.57 × 10−3 and +1.9 × 10−3 for 3Δ and 3Λ, respectively. The significant difference in CPL magnitude between 3Δ and 3Λ likely arises from interligand interactions (edge-to-face arrangement versus strong π-π interaction) for the pendant phenyl ring of the BOX-CN ligand which differ for the two isomers.

Synthesis, Structures, Optical, and Electrochemical Properties of Bis-Cyclometallated Iridium(III) Complexes with N-Benzylbenzimidazoles

Synthesis, Structures, Optical, and Electrochemical Properties of Bis-Cyclometallated Iridium(III) Complexes with N-Benzylbenzimidazoles

Triplet-Triplet Energy Transfer in Bis-Cyclometalated Iridium Complexes with Pyrene-Substituted Isocyanides.

Nonlinear optical (NLO) materials are able to modulate responses of electromagnetic radiation, leading to phenomena critical to modern telecommunications technologies. The last two decades have seen significant advances in the area of molecular nonlinear chromophores, particularly with respect to reverse-saturable absorption (RSA). Here, we introduce a strategy for intense excited-state absorption (ESA) that involves bis-cyclometalated iridium complexes with isocyanide ancillary ligands decorated with pyrene triplet acceptors. Upon excitation, the complexes undergo rapid triplet-triplet energy transfer (TTET) to the acceptor excited states. This report describes five bis-cyclometalated iridium complexes using two different pyrene-substituted isocyanides with the general formula [Ir(C^N)2(CNAr)2]PF6 (C^N = cyclometalating ligand, CNAr = isocyanide ancillary ligand: CNArpyr = 2,6-dimethyl-4-(1-pyrenyl)phenyl isocyanide, CNpyr = 1-pyrenyl isocyanide). The synthesized complexes were thoroughly characterized via 1H and 13C{1H} NMR spectroscopy, Fourier-transform Infrared spectroscopy, and electrospray ionization mass spectrometry. The excited states were evaluated with UV-vis absorption, steady-state and time-resolved photoluminescence, and transient absorption spectroscopy. Phosphorescence is completely quenched at room temperature, but in the solvent glass matrix at 77 K, there is luminescence originating from a π → π* triplet state on the pyrene moiety, abbreviated herein as 3pyrene. All five complexes display intense and long-lived ESA originating from the 3pyrene state. The localization of the ground-state absorption on the cyclometalating ligands and the excited-state absorption on the pyrene moiety allows for independent tuning of ground-state absorption (GSA) and ESA to optimize RSA and other NLO attributes.

Enhanced Deep-Red Phosphorescence in Cyclometalated Iridium Complexes with Quinoline-Based Ancillary Ligands.

Compounds with good photoluminescence quantum yields (ΦPL) in the deep-red to near-infrared parts of the spectrum are desired for a variety of applications in optoelectronics, imaging, and sensing. However, in this region of the spectrum, quantum yields are usually modest, which is explained by the energy gap law and the inherently slower radiative decay rates for low-energy emitters according to the second-order perturbation theory. In this work, we outline a new direction in deep-red luminescence, introducing a new suite of bis-cyclometalated iridium complexes with efficient luminescence beyond 650 nm. Seven new complexes are prepared using two different cyclometalating (C^N) ligands with four quinoline-derived ancillary ligands (L^X). The chosen cyclometalating ligands are well-established to produce deep-red phosphorescence and include a metalated phenyl ring appended to a conjugated heterocycle. The ancillary ligands combine a rigid quinoline or benzoquinoline "L" donor with a variable anionic "X" donor comprised of an O-donor aryloxy or carboxylate or an N-donor amidate. These complexes phosphoresce in the deep-red region with wavelengths between 650 and 700 nm and solution quantum yields between 0.018 and 0.42.

Evaluation of a trinuclear heteroleptic bis-cyclometalated iridium(III) complex as a photoredox catalyst for visible light-mediated hydrothiolation reactions

A trinuclear bis-cyclometalated iridium(III) polypyridyl complex was synthesised and evaluated as a photoredox catalyst for visible light- mediated thiol-ene coupling reactions. Electronic absorption and emission studies revealed that the complex shows a blue-shifted emission spectrum, with a wavelength at 578 nm, relative to the canonical iridium complex, [Ir(ppy)3] (598 nm). The emissions are attributed to the transition from the triplet MLCT excited state (3MLCT) to the ground state. Cyclic voltammetry studies demonstrated that this complex is a promising candidate for the photoredox catalysed reactions, with the trinuclear iridium complex increasing the oxidation potential without sacrificing the reduction ability. The iridium(III) complex was evaluated as a photoredox catalyst in the model hydrothiolation coupling reaction and benchmarked against a trinuclear ruthenium congener. Reactions conducted with the trinuclear iridium polypyridyl complex resulted in the highest NMR yields.

Substituent-Dependent Azide Addition to Isocyanides Generates Strongly Luminescent Iridium Complexes.

Ligand-centered functionalization reactions offer diverse strategies to prepare luminescent organometallic compounds. These compounds can have unique structures that are not accessible via traditional coordination chemistry and can possess enhanced or unusual photophysical properties. Here we show that bis-cyclometalated iridium bis-isocyanide complexes (1) react with azide (N3-) to form novel luminescent structures. The fate of the reaction with azide is determined primarily by the substituent on the aryl isocyanide. Those with electron-withdrawing substituents (CF3 or NO2) react with 1 equiv of azide followed by N2 extrusion, forming aryl cyanamido products (2). With electron-donating groups on the aryl isocyanide the reactivity is more diverse, and three outcomes are possible. In two cases, the isocyanide and azide undergo a [3 + 2] cycloaddition to form a C-bound tetrazolato structure (3). In three other cases, 2 equiv of azide are involved in the formation of a previously unobserved structure, where a tetrazolato and aryl cyanamido couple and rearrange to form a chelating ligand comprised of an N-bound tetrazolato and an acyclic diaminocarbene (4). Finally, a bimetallic aryl cyanamido complex (5) is isolated in one case. All compounds are luminescent, some with exceptional photoluminescence quantum yields as high as 0.81 in solution for sky-blue emission, and 0.87 for yellow emission and 0.65 for orange-red emission in polymer films.

Panchromatic Excited-State Absorption in Bis-Cyclometalated Iridium Isocyanide Complexes.

In this work, we introduce a series of cyclometalated iridium complexes and evaluate the suitability of this class of compounds in nonlinear optical (NLO) applications, with an emphasis on long-lived, panchromatic reverse-saturable absorption (RSA). The investigated complexes are represented by the general formula [Ir(C^N)2(CNArdmp)2]+, (C^N = cyclometalating ligand, CNArdmp = 2,6-dimethylphenyl isocyanide). Seven such complexes were synthesized and characterized, including in-depth analysis of their photophysical properties (UV-vis absorption, photoluminescence, and transient absorption). This series of compounds contains seven different cyclometalating ligands (2-phenylbenzothiazole (bt) (Ir1), 5-nitro-2-phenylpyridine (ppyNO2) (Ir2), 5-nitro-2-(9-phenanthryl)pyridine (phenNO2) (Ir3), 2-(benzo[b]thiophen-2-yl)quinoline (btq) (Ir4), 6-(benzo[b]thiophen-2'-yl)phenanthridine (btph) (Ir5), 2,4-diphenylquinoline (dpq) (Ir6), and 6-nitro-2,4-diphenylquinoline (NO2dpq) (Ir7)), which have profound effects on their ground-state and excited-state absorption spectra. To evaluate the effects of the isocyanide ancillary ligands, some heteroleptic bis-cyclometalated iridium(III) acetylacetonate (acac) analogue complexes are included as points of comparison. In the ground state, the bis-isocyanide complexes display UV-vis absorption with the characteristic 1LC (π → π*) band at λ < 350 nm and 1MLCT bands at 350-500 nm. Five of the complexes (Ir1, Ir2, Ir4, Ir5, and Ir6) display broad, intense triplet excited-state absorption with no ground-state bleach (GSB) over the spectral window of 400-900 nm, with excited-state lifetimes spanning three orders of magnitude from ∼32 ns to 12 μs. The photophysical data suggests that the isocyanide ancillary ligand blue-shifts the GSB transient into the UV, which is normally found in the middle of the visible region for cyclometalated iridium complexes. This study demonstrates the applicability of cationic cyclometalated iridium(III) bis-isocyanide complexes as candidate RSA materials.

Modulation of the oxygen sensing properties of iridium (III) complexes by changing their substitution groups

In this study, new bis-cyclometalated iridium (III) complexes bearing different ligated groups (–H, –OCH3, –F, –CH3) at the aryl moiety (Ir-1, Ir-2, Ir-3 and Ir-4) were synthesized and characterized. Then oxygen sensing properties of corresponding complexes were investigated in EC film. The complexes showed room temperature phosphorescence spectra in the range of 562–590 nm in THF and 546–554 nm in ethyl cellulose (EC) matrix. When they were incorporated in an ethyl cellulose matrix, the probes showed optimal dynamics of luminescence for oxygen monitoring in the range from 0 % to 100 % air saturation. The I0/I100 values of Ir-1, Ir-2, Ir-3 and Ir-4 in EC thin film were calculated as 10.9, 5.0, 7.3 and 22.7, respectively. The results showed that the oxygen sensitivity accomplishment of the complex core can be fine-tuned by varying these ligated groups, and the weak electron-donating properties of the methyl groups at the aryl moiety improve remarkably the optical oxygen sensing abilities of the Iridium (III) complexes.

New Bis-Cyclometalated Iridium(III) Complexes with β-Substituted Porphyrin-Arylbipyridine as the Ancillary Ligand: Electrochemical and Photophysical Insights.

An efficient synthetic access to new cationic porphyrin-bipyridine iridium(III) bis-cyclometalated complexes was developed. These porphyrins bearing arylbipyridine moieties at β-pyrrolic positions coordinated with iridium(III), and the corresponding Zn(II) porphyrin complexes were spectroscopically, electrochemically, and electronically characterized. The features displayed by the new cyclometalated porphyrin-bipyridine iridium(III) complexes, namely photoinduced electron transfer process (PET), and a remarkable efficiency to generate 1O2, allowing us to envisage new challenges and opportunities for their applications in several fields, such as photo(catalysis) and photodynamic therapies.

Trimetallic Iridium-Nickel-Iridium Bis(formazanate) Assemblies.

Formazans have attracted a lot of attention in coordination chemistry since the early 1940s because of their unique properties engendered by the nitrogen-rich conjugated backbone. Although many studies have been done using formazanates to chelate transition metals, research using formazanates as building blocks for polynuclear compounds and supramolecular chemistry remains rare. In this paper, we describe a synthetic strategy that uses a pyridyl-substituted bis(formazanato)nickel complex as a metalloligand to further assemble with two [Ir(C^N)2]+ centers (C^N is the cyclometalating ligand). The trimetallic complexes represent a new binding mode for flexidentate pyridyl-substituted formazanates and a new structural class of polynuclear formazanate complexes. This work expands the chemistry of polynuclear formazanate complexes, for the first time pairing 3d and 5d metals in the same assembly. The redox chemistry of these trimetallic complexes, evaluated via cyclic voltammetry, is described. The compounds described in this work are luminescent, and studies of bis-cyclometalated iridium model complexes lacking the formazanate bridge confirm that the phosphorescence arises from the iridium center.

Synthesis and Characterization of Heteroleptic Bis-Cyclometalated Iridium(III) Complexes

• Heteroleptic bis-cyclometalated Ir(III)-NHC complexes were synthesized. • The reaction system is simple and easy to be handled. • The iridium(III) complexes exhibited photoluminescence and fluorescence lifetimes. Several heteroleptic bis-cyclometalated iridium(III) complexes containing ancillary N-heterocyclic carbene ligands were synthesized in medium to good yields under mild reaction environment. The desired Ir(III) complexes have been characterized by nuclear magnetic resonance spectroscopy, electronic absorption, emission spectroscopy, cyclic voltammetry and fourier transform infrared spectrum (FT-IR). Each of the [(C ˄ N) 2 Ir(NHC)] complexes exhibited strong photoluminescence with quantum yields ( ϕ PL ) ranging from 1.35% to 41.41% and fluorescence lifetimes around 43 ns in dichloromethane solution at room temperature. These results showed that the electrochemical and photophysical properties of heteroleptic bis-cyclometalated iridium(III) complexes were analogous, furthering the conclusion that the electronic structure and excited-state dynamics were not influenced by auxiliary ligands modification.

Effects of Ancillary Ligands on Deep Red to Near-Infrared Cyclometalated Iridium Complexes.

The design of organometallic compounds with efficient phosphorescence in the deep red to near-infrared portions of the spectrum is a long-standing fundamental challenge. Here we describe a series of heteroleptic bis-cyclometalated iridium complexes with phosphorescence in these low-energy regions of the spectrum. The cyclometalating ligands in this study feature a metalated benzothiophene aryl group substituted with a quinoline, isoquinoline, or phenanthridine heterocycle. Increasing the conjugation on the heterocycle stabilizes the ligand-centered LUMO, decreases the HOMO-LUMO gap, and enables phosphorescence to occur at long wavelengths. These cyclometalating ligands are paired with a variety of electron-rich ancillary ligands, such as dithiocarbamate (dipdtc), β-ketoiminate (acNac), β-diketiminate (NacNac), amidinate (dipba), and hexahydropyrimidopyrimidine (hpp), some of which have significant influences on the phosphorescence wavelength and excited-state dynamics. The syntheses of seven compounds in this series are described, three of which are structurally validated by single-crystal X-ray diffraction. Cyclic voltammetry reveals the effects of ligand modification on the frontier orbital energies. The photophysical properties of all compounds are thoroughly characterized by UV-vis absorption spectroscopy and steady-state photoluminescence at room-temperature and 77 K. Photoluminescence quantum yields and lifetimes of all compounds are reported.

Enhanced deep red to near-infrared (DR-NIR) phosphorescence in cyclometalated iridium(iii) complexes

Bis-cyclometalated iridium complexes with highly conjugated cyclometalating ligands and electron-rich ancillary ligands have exceptional quantum yields for deep-red to near-infrared phosphorescence.

Efficient Photogeneration of Hydrogen Boosted by Long-Lived Dye-Modified Ir(III) Photosensitizers and Polyoxometalate Catalyst

Efficient Photogeneration of Hydrogen Boosted by Long-Lived Dye-Modified Ir(III) Photosensitizers and Polyoxometalate Catalyst

Bis-Cyclometalated Indazole and Benzimidazole Chiral-at-Iridium Complexes: Synthesis and Asymmetric Catalysis.

A new class of bis-cyclometalated iridium(III) catalysts containing two inert cyclometalated 6-tert-butyl-2-phenyl-2H-indazole bidentate ligands or two inert cyclometalated 5-tert-butyl-1-methyl-2-phenylbenzimidazoles is introduced. The coordination sphere is complemented by two labile acetonitriles, and a hexafluorophosphate ion serves as a counterion for the monocationic complexes. Single enantiomers of the chiral-at-iridium complexes (>99% er) are obtained through a chiral-auxiliary-mediated approach using a monofluorinated salicyloxazoline and are investigated as catalysts in the enantioselective conjugate addition of indole to an α,β-unsaturated 2-acyl imidazole and an asymmetric Nazarov cyclization.

β-Diketiminate-supported iridium photosensitizers with increased excited-state reducing power

Triazole and NHC-based bis-cyclometalated iridium β-diketiminate complexes emerge as some of the strongest reported visible-light photoreductants. Fast photoinduced electron transfer and photoredox catalysis on organohalide substrates are observed.