Bis-cyclometalated Iridium Complexes Research Articles

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.

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.

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

Tuning the NLO response of bis-cyclometalated iridium(iii) complexes by modifying ligands: experimental and structural DFT analysis

DFT calculations have been carried out to investigate two synthesized iridium(iii) complexes with substituted Phbd (1-phenyl-2-(pyridin-2-yl)-1H-benzo[d]imidazole) and Crbd (9-(4-(2-(pyridin-2-yl)-1H-benzo[d]imidazol-1-yl)phenyl)-9H-carbazole) as ancillary ligands.

Second-order NLO properties of bis-cyclometalated iridium(III) complexes with β-diketiminate ancillary ligand: Substituent and redox effect

Density functional theory (DFT) calculations have been carried out to investigate the switching of the second-order nonlinear optical (NLO) properties of iridium(III) complexes. The aim of this paper is to calculate the substituent effect and redox effect on geometrical and electronic structures, redox center, UV–Vis absorption spectra and second-order nonlinear optical (NLO) properties. It is found that changing β-diketiminate ancillary ligand have little effect on first hyperpolarizabilities values, but the redox process can significantly enhance the second-order NLO responses. The βtot values of 1+,2+and3+oxidation states of the complexes are about 10.2 times, 19.7 times and 25.5 times larger than their corresponding neutral complexes, respectively. The βtot values of the complexes in their various reduction states 1-, 2- and 3- are about 13.2 times, 35.0 times and 8.5 times larger than neutral complexes, respectively. The complexes in their various reduction or oxidation states display larger first hyperpolarizabilities than neutral complexes due to the remarkable bathochromic shift of maximal absorption and the decrease of related transition energies. The theoretical investigation of these iridium complexes will be helpful for providing a fundamental guideline and reference for further research for novel NLO materials.

Bis-Cyclometalated Iridium Complexes Containing 4,4'-Bis(phosphonomethyl)-2,2'-bipyridine Ligands: Photophysics, Electrochemistry, and High-Voltage Dye-Sensitized Solar Cells.

In this report, the synthesis and characterization of two bis-cyclometalated iridium(III) complexes are presented. Single-crystal X-ray diffraction shows that [Ir(ppy)2(4,4'-bis(diethylphosphonomethyl)-2,2'-bipyridine)]PF6 adopts a pseudooctahedral geometry. The complexes have an absorption feature in the near-visible-UV region and emit green light with excited-state lifetimes in hundreds of nanoseconds. The redox properties of these complexes show reversible behavior for both oxidative and reductive events. [Ir(ppy)2(4,4'-bis(phosphonomethyl)-2,2'-bipyridine)]PF6 readily binds to metal oxide supports, like nanostructured SnIV-doped In2O3 and TiO2, while still retaining reversible redox chemistry. When incorporated as the photoanode in dye-sensitized solar cells, the devices exhibit open-circuit voltages of >1 V, which is a testament to their strength of these iridium(III) complexes as photochemical oxidants.

Redox-Active Bis-Cyclometalated Iridium(III) Complex as a DNA Photo-Cleaving Agent.

The development of new photoactive metal complexes that can trigger oxidative damages to the genetic material is of great interest. In the present paper, we describe the detailed study of a highly photo-oxidant iridium(III) complex that triggers photoinduced electron transfer (PET) with purine DNA bases. The PET has been studied by luminescence and laser flash photolysis experiments. From plasmid DNA agarose gel electrophoresis experiments, we demonstrated the high ability of the iridium complex to induce strand breaks upon light irradiation. Reactive oxygen species (ROS)-specific scavengers and stabilizers were employed to identify that the photocleavage process, the results of which infer singlet oxygen and hydrogen peroxide as the predominant species. To the best of our knowledge, the present work represents one of the few study for highly photo-oxidant bis-cyclometalated iridium(III) complex toward DNA.

Efficient near-infrared luminescence from bis-cyclometalated iridium(iii) complexes with rigid quinoline-derived ancillary ligands

Five new near-infrared (NIR) phosphorescent bis-cyclometalated iridium(iii) complexes, partnering highly conjugated cyclometalating ligands with quinoline-derived ancillary ligands, have been developed. These complexes have peak NIR luminescence wavelengths from 711 to 729 nm, with photoluminescence quantum yields ranging from 0.042 to 0.36.

Improved deep-red phosphorescence in cyclometalated iridium complexes via ancillary ligand modification

Bis-cyclometalated iridium complexes with electron-rich ancillary ligands exhibit high phosphorescence quantum yields in the deep red region.

Blue-phosphorescent bis-cyclometalated iridium complexes with aryl isocyanide ancillary ligands

The design of organometallic complexes with efficient blue phosphorescence remains a challenge in the field of optoelectronics. This paper describes a series of eight cationic, isocyanide-ligated bis-cyclometalated iridium complexes of the general formula [Ir(C^Y)2(CNAr)2](PF6), where C^Y is a triazole-based C^N cyclometalating ligand or an NHC-based C^C: cyclometalating ligand, and CNAr is an aryl isocyanide. The triazole- and NHC-derived cyclometalating ligands, in combination with the π-acidic isocyanide ancillary ligands, result in large HOMO–LUMO gaps and engender these compounds with photoluminescence in the blue region of the spectrum. The complexes are synthesized by a general synthetic procedure and isolated in moderate to good isolated yields, with a combination of NMR spectroscopy, mass spectrometry, and X-ray crystallography (for six of the eight compounds) establishing the identity and bulk purity of each compound. The redox properties of the compounds are studied by cyclic voltammetry, which provide evidence for the large HOMO–LUMO gaps that are critical for the blue photoluminescence. The triazole-based compounds are weakly luminescent in fluid solution at room temperature, and all complexes luminesce at 77 K in frozen solvent glass or at room temperature when immobilized in a transparent poly(methyl methacrylate) (PMMA) film. CIE coordinates for the photoluminescence spectra indicate pure blue emission for all compounds, with CIEy ≤ 0.15 for all but one compound.

Synthesis and Characterization of High-Efficiency Red Phosphorescent Iridium(III) Complexes with 1-(4-(Trifluoromethyl)phenyl)isoquinoline Ligand

Two new tfmpiq-based bis-cyclometalated iridium(III) complexes, [(tfmpiq)2Ir(imdzppo)] (2a) and [(tfmpiq)2Ir(idzpo)] (2b) (where tfmpiq = 1-(4-(trifluoromethyl)phenyl)isoquinoline, imdzppo = 2-(imidazo[1,2-a]pyridin-2-yl)phenol, idzpo = 2-(2H-indazol-2-yl)phenol), have been synthesized and fully characterized. The single crystal structure of 2b has been determined. The relationship between the structures and photophysical properties of both complexes are considered, and the DFT calculations have been used to further support the deduction. These Ir(III) complexes emit red light with quantum yields of 39.9-51.9% in degassed CH2Cl2 solution at room temperature. Also, their emission originates from a hybrid 3MLCT/3LLCT/3LC excited state. All these results show that iridium(III) complexes 2a-2b are suitable for red-phosphorescent materials in OLEDs.

Targeting G-Rich DNA Structures with Photoreactive Bis-Cyclometallated Iridium(III) Complexes.

The synthesis and characterisation of three novel iridium(III) bis-cyclometallated complexes is reported. Their photophysics have been fully characterised by classical methods and revealed charge-transfer (CT) and ligand-centred (LC) transitions. Their ability to selectively interact with G-quadruplex telomeric DNA over duplex DNA has been studied by circular dichroism (CD), bio-layer interferometry (BLI) and surface plasmon resonance (SPR) analyses. Interestingly, one of the complexes was able to promote photoinduced electron transfer (PET) with the guanine DNA base, which in turn led to oxidative damage (such as the formation of 8-oxoguanine) to the telomeric sequence. To the best of our knowledge, this is the first study of highly photo-oxidising bis-cyclometallated iridium(III) complexes with G-quadruplex telomeric DNA.