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In this minireview, a state of the art of the NHC transition metal complexes applied in two different modern technologies for lightening applications, namely Organic Light Emitting Diodes (OLEDs) and Light-Emitting Electrochemical Cells (LECs), is presented. In each technology, the different transition metal centres studied are described and the advantages brought by the NHC ligands in terms of electronic and steric properties is discussed. Devices obtained with these complexes are also presented and the stability and their efficiencies are also highlighted. [ABSTRACT FROM AUTHOR]

Nowadays, the design and development of novel phosphorescent iridium(III) complexes for various optoelectronic applications is a well-recognized area of research. The fascinating photophysical properties of iridium(III) compounds are strongly influenced by the spin-orbit coupling exerted by the iridium(III) core, usually resulting in intense emissions with short excited-state lifetimes, which can be precisely controlled with the aid of molecular engineering of the chelating ligand. This review focuses on the recent developments and state of the art knowledge on phosphorescent iridium(III) compounds, especially on heteroleptic complexes derived from 2,3′-bipyridine class of cyclometalating and ancillary ligands, highlighting the excited state phenomenon behind their emission behavior. [ABSTRACT FROM AUTHOR]

The synthesis of four cyclometallated [Ir(C^N)2(N^N)][PF6] compounds in which N^N is a substituted 2,2′-bipyridine (bpy) ligand and the naphthyl-centred ligand 2,7-bis(2-(2-(4-(pyridin-2-yl)phenoxy)ethoxy)ethoxy)naphthalene provides the two cyclometallating C^N units is reported. The iridium(iii) complexes have been characterized by 1H and 13C NMR spectroscopies, mass spectrometry and elemental analysis, and their electrochemical and photophysical properties are described. Comparisons are made with a model [Ir(ppy)2(N^N)][PF6] compound (Hppy = 2-phenylpyridine). The complexes containing the naphthyl-unit exhibit similar absorption spectra and excitation at 280 nm leads to an orange emission. The incorporation of the naphthalene unit does not lead to a desirable blue contribution to the emission. Density functional theory calculations were performed to investigate the geometries of the complexes in their ground and first triplet excited states, as well as the energies and compositions of the highest-occupied and lowest unoccupied molecular orbital (HOMO and LUMO) manifolds. Trends in the HOMO–LUMO gaps agree with those observed electrochemically. The energy difference between the LUMO and the lowest unoccupied MO located on the naphthyl unit (LUMO+7) is large enough to explain why there is no contribution from the naphthyl-centred triplet excited state to the phosphorescence emission. Singlet excited states were also investigated. Light-emitting electrochemical cells (LECs) using the [Ir(C^N)2(N^N)][PF6] and [Ir(ppy)2(N^N)][PF6] complexes in the emissive layer were made and evaluated. The presence of the naphthyl-bridge between the cyclometallating units does not significantly alter the device response. [ABSTRACT FROM AUTHOR]

Light-Emitting Electrochemical Cells (LECs) with a simple device structure ITO/Ru complex/Ga:In were prepared by using heteroleptic ruthenium(ii) complexes containing 2-(2-hydroxyphenyl)-1-(4-bromophenyl)-1h-imidazo[4,5-f][1,10]phenanthroline (hpbpip) as the π-extended ligand. After ancillary ligand modification, the [Ru(hpbpip)(dmbpy)2](ClO4)2 complex shows a deep red electroluminescence emission (2250 cd m−2 at 6 V) centered at 685 nm, 65 nm red-shifted compared to the [Ru(bpy)3](ClO4)2 benchmark red-emitter at a very low turn voltage (2.6 V), demonstrating its potential for low-cost deep-red light sources. Moreover, the PL quantum yield of the [Ru(hpbpip)(bpy)2](ClO4)2 complex was revealed to be higher (0.121) than the benchmark standard [Ru(bpy)3]2+ (0.095). [ABSTRACT FROM AUTHOR]

The synthesis, structures and photophysical properties of a series of bis-cyclometallated Ir(iii) complexes bearing phenylpyrazole (ppz) cyclometallating ligands and phenanthroline-based ancillary ligands containing thienyl- and bithienylamido groups are reported. All complexes are emissive in solution, while in PMMA films strong emission is observed from the thienylamido substituted complex with no emission from the bithienylamido complex. The bithienylamido substituted complex has an excited state lifetime which is significantly longer than the emission lifetime, attributed to the population of non-equilibrated 3MLCT and 3LC states in this complex. This represents a rare example of this unusual excited state behaviour. DFT calculations show that the emitting 3MLCT state and the dark 3LC state on bithiophene are close in energy and that a large change in the triplet state geometry occurs upon excitation that effectively lowers the energy of the 3MLCT state below that of the dark 3LC state. The low quantum yield of the bithienylamido complex is attributed to a structural rearrangement upon relaxation back to the ground state, opening a non-radiative decay pathway. [ABSTRACT FROM AUTHOR]

Green- and yellow-emitting cationic iridium complexes, [Ir(dfppy) 2 (pybi)]PF 6 (Complex 1) and [Ir(ppz) 2 (pybi)]PF 6 (Complex 2), were synthesized using 2-(2,4-difluorophenyl)pyridine (Hdfppy) and 1-phenylpyrazole (Hppz) as the cyclometalating ligands and 2-(2-pyridyl)benzimidazole (pybi) as the ancillary ligand. In order to gain insight into the photophysical and electrochemical behavior, density functional theory (DFT) calculations were simulated on the above complexes, which showed consistency in energy gaps obtained from both experimental and theoretical results. Light-emitting electrochemical cells (LECs) based on Complex 1 were obtained by solution-processed fabrication, and they showed green (523 nm) electroluminescence with Commission Internationale de L'Eclairage (CIE) coordinates of (0.33, 0.58); on the other hand, the LEC utilizing Complex 2 showed yellow electroluminescence with CIE coordinates of (0.41, 0.56). The highest luminance of 1492 cd m −2 and current density of 83.13 mA cm −2 were achieved for the LEC utilizing Complex 2, owing to the more balanced carrier injection and recombination as compared to those for Complex 1. The negative role of the free – NH group in the electroluminescent properties of LECs is confirmed by comparing the current results with those previously reported for N-alkylated benzimidazole moieties. [ABSTRACT FROM AUTHOR]

Light-emitting electrochemical cells (LECs) are a promising type of electroluminescent device for display and lighting applications. In this study, LECs based on ionic iridium complexes utilizing a tetrazole based ancillary ligand were fabricated and their electrical properties were investigated. Two new iridium(III) complexes with tetrazole based ancillary ligands, namely, [Ir(ppy)(tetrazole)]PF (complex 1) and [Ir(dfppy)(tetrazole)]PF (complex 2) (where ppy is 2-phenylpyridine, dfppy is 2-(2,4-difluorophenyl)pyridine, tetrazole is 5-bromo-2-(2-methyl-2H-tetrazol-5-yl)-pyridine and PF is hexafluorophosphate), have been synthesized and characterized. These synthesized complexes were used for the fabrication of LEC devices. LECs based on complex 1 result in orange light emission (576 nm) with the Commission Internationale de l'Eclairage (CIE) coordinates of (0.45, 0.49), while complex 2 emits green (518 nm) electroluminescence with the CIE coordinates of (0.33, 0.49). Our work suggests that the light emission of cationic iridium complexes can easily be tuned by the substituents on the cyclometalated ligands. [ABSTRACT FROM AUTHOR]

Four cationic iridium(III) complexes of the form [Ir(CN)2(NN)]+ bearing either a 2,5-dipyridylpyrazine (2,5-dpp) or a 2,2':5',2''-terpyridine (2,5-tpy) ancillary ligand and either 2-phenylpyridine (ppy) or a 2-(2,4-difluorophenyl)-5-methylpyridine (dFMeppy) cyclometalating ligands were synthesized. The optoelectronic properties of all complexes have been fully characterized by UV-visible absorption, cyclic voltammetry and emission spectroscopy. The conclusions drawn from these studies have been corroborated by DFT and TDDFT calculations. The four complexes were assessed as emitters in light-emitting electrochemical cells. Complex 1a, [Ir(ppy)2(2,5-dpp)]PF6, was found to be a deep red emitter (666 nm) both in acetonitrile solution and in the electroluminescent device. Complex 2a, [Ir(ppy)2(2,5-tpy)]PF6 was found to be an orange emitter (604 nm) both in solution and in the LEEC. LEECs incorporating both of these complexes were stable over the course of around 4-6 hours. Complex 1b, [Ir(dFMeppy)2(2,5-dpp)]PF6, was also determined to emit in the orange (605 nm) but with a photoluminescent quantum yield (ΦPL) double that of 2a. Complex 2b, [Ir(dFMeppy)2(2,5-tpy)]PF6 is an extremely bright green emitter (544 nm, 93%). All four complexes exhibited quasireversible electrochemistry and all four complexes phosphoresce from a mixed charge-transfer excited state. [ABSTRACT FROM AUTHOR]

A dynamic-covalent metal-containing polymer was synthesized by the condensation of linear diamine and dialdehyde subcomponents around copper(I) templates in the presence of bidentate phosphine ligands. In solution, the red polymers undergo a sol-gel transition upon heating to form a yellow gel, a process that can be either reversible or irreversible depending on the solvent used. When fabricated into a light-emitting electrochemical cell (LEC), the polymer emits infrared light at low voltage. As the voltage is increased, a blue shift in the emission wavelength is observed until yellow light is emitted, a process which is gradually reversed over time upon lowering the voltage. The mechanism underlying these apparently disparate responses is deduced to be due to loss of the copper phosphine complex from the polymer. [ABSTRACT FROM AUTHOR]

A dynamic-covalent metal-containing polymer was synthesized by the condensation of linear diamine and dialdehyde subcomponents around copper(I) templates in the presence of bidentate phosphine ligands. In solution, the red polymers undergo a sol-gel transition upon heating to form a yellow gel, a process that can be either reversible or irreversible depending on the solvent used. When fabricated into a light-emitting electrochemical cell (LEC), the polymer emits infrared light at low voltage. As the voltage is increased, a blue shift in the emission wavelength is observed until yellow light is emitted, a process which is gradually reversed over time upon lowering the voltage. The mechanism underlying these apparently disparate responses is deduced to be due to loss of the copper phosphine complex from the polymer. [ABSTRACT FROM AUTHOR]

Highlights: [•] Cationic iridium complexes were synthesized using imidazole based ancillary ligand. [•] Light-emitting electrochemical cells (LECs) were fabricated and characterized. [•] LECs based on these complexes resulted in green and blue–green light emission. [•] Imidazole based ancillary ligands are good candidate to destabilize LUMO orbitals. [ABSTRACT FROM AUTHOR]

The photophysical and optical properties of a series of charged biscyclometalated [Ir(ppyn)2(N∧Nn)]+ complexes have been investigated with density functional theory, where ppy0 = 2-phenylpyridine; ppy1 = 2-(2,4-difluorophenyl)pyridine; N∧N = 2-(1-phenyl-1H-pyrazol-3-yl)pyridine (1a, 1b); 2-(4-phenyl-1Himidazol- 2-yl)pyridine (2a, 2b); 2-(1,4-diphenyl-1H-imidazol-2-yl)pyridine (3a, 3b); 2-(2-phenyl-2H- 1,2,3-triazol-4-yl)pyridine (4a, 4b); 2-(1-phenyl-1H-1,2,4-triazol-3-yl)pyridine (5a, 5b); 2-(3-(pyridin- 2-yl)-1H-1,2,4-triazol-1-yl)pyridine (6a, 6b); 2-(1H-pyrazol-1-yl)pyridine (7a, 7b), respectively. The calculated results reveal that both the difluoro-substituent and the different 2-pyridyl azolate ancillary ligands have a large influence on tuning the emission energies and quantum yields of the studied complexes. On the basis of the results reported herein, we attempt to explain the experimental observation that the complexes 7a and 7b show high quantum phosphorescence efficiency (ΦPL) of 23% and 20% compared with 1a with ΦPL of 3%. To clarify this behavior, the metal-to-ligand charge transfer contributions (MLCT%), the S1-T1 splitting energy (ΔES1-T1) and the transition dipole moment (μS1) upon the S0-S1 transition were calculated. Drastically small ΔES1-T1 and large MLCT% for 7a (0.06 eV and 28.2%, respectively) and 7b (0.08 eV and 24.6%, respectively) compared to those for 1a (0.60 eV and 19.5%, respectively) account for their relatively high ΦPL observed experimentally. Besides, the remarkably small ΔES1-T1, large MLCT% and similar μS1 for 2a (0.04 eV, 29.1% and 0.026 D, respectively) compared with those for 2b (0.56 eV, 2.3% and 0.022 D, respectively) could be interpreted by the difluoro-substituent effects. Furthermore, 2a-4a and 4b-5b are considered to have relatively better physical properties with respect to the experimentally synthesized complexes 7a, 7b and 1a. Therefore, the newly designed complexes 2a-4a and 4b-5b are expected to be highly efficient sky-blue and blue-green emitters for LEC application. [ABSTRACT FROM AUTHOR]

Light-emitting electrochemical cells (LECs) with a simple device structure were prepared by using heteroleptic bis(tridentate) ruthenium(II) complexes [ 1](PF6)2-[ 3](PF6)2 as emitters. The push-pull substitution shifts the emission energy to low energy, into the NIR region. The devices emit deep red light up to a maximum emission wavelength of 755 nm [CIE (International Commission on Illumination) coordinates: x = 0.731, y = 0.269 for [ 3](PF6)2], which, to the best of our knowledge, is the lowest emission energy for LECs containing bis(tridentate) ruthenium(II) complexes. A device structure of ITO/PEDOT:PSS/ruthenium(II) complex/Ag was used, and the thickness of the emitting layer was measured by AFM [ITO: indium tin oxide, PEDOT: poly(3,4-ethylenedioxythiophene), PSS: poly(styrenesulfonate), AFM: atomic force microscopy]. To enhance the external quantum efficiency (EQE), cells were fabricated with and without poly(methyl methacrylate) (PMMA) as additive in the emitting layer. [ABSTRACT FROM AUTHOR]

Inlight-emitting electrochemical cells, the lifetime of the deviceis intrinsically linked to the stability of the phosphorescent emitter.In this study, we present a series of ionic iridium(III) emittersbased on cyclometalating phenylpyridine ligands whose fluorine substituentsare varied in terms of position and number. Importantly, despite thesestructural modifications, the emitters exhibit virtually identicalelectrochemical and spectroscopic properties, which allows for propercomparison in functional devices. Quantum-chemical calculations supportthe properties measured in solution and suggest great similaritiesregarding the electronic structures of the emitters. In electroluminescentdevices, the initial luminance, efficiency, and efficacy are alsorelatively unaffected throughout the series. However, a shorter devicelifetime is obtained upon increasing the fluorine content of the emitter,which suggests drawbacks of such electron-withdrawing substituentsfor the design of ionic iridium(III) emitters. [ABSTRACT FROM AUTHOR]

Abstract: Green and yellow light emitting phosphorescent iridium complexes with 5-methyl-1,10-phenanthroline as an ancillary ligand were synthesized and characterized for the fabrication of light-emitting electrochemical cells (LECs). The photophysical and electrochemical properties of the resulting complexes, [Ir(dfppy)2(Me-phen)]PF6 (1) and [Ir(ppz)2(Me-phen)]PF6 (2) (where dfppy=2-(2,4-difluorophenyl)pyridine; ppz=1-phenylpyrazole, Me-phen=5-methyl-1,10-phenanthroline) were investigated by means of UV–Vis absorption, fluorescence spectroscopy and cyclic voltammetry. Density functional theory (DFT) calculations were performed to gain insight into the photophysical and electrochemical behaviors and to determine the electronic energy levels for the complexes. LECs were fabricated based on these complexes and their electroluminescent properties were investigated, which resulted in a maximum luminance of 2430 and 1549cdm−2 for complexes 1 and 2 respectively. LECs incorporating these heteroleptic complexes effectively tuned the emission color through the meticulous selection of the cyclometallated ligands and they displayed highly luminescent green and yellow electroluminescence with the Commission Internationale de L’Eclairage (CIE) coordinates of (0.25, 0.58) and (0.42, 0.54) for complexes 1 and 2 respectively. [Copyright &y& Elsevier]

Abstract: Highly luminescent light-emitting electrochemical cells (LECs) based on cationic iridium complexes [Ir(ppz)2(dpphen)]PF6 (1) and [Ir(ppz)2(tmphen)]PF6 (2) (ppz is 1-phenylpyrazole, dpphen is 4,7-diphenyl-1,10-phenanthroline and tmphen is 3,4,7,8-tetramethyl-1,10-phenanthroline) with phenanthroline based ancillary ligands were fabricated using air stable electrodes and their electroluminescent properties were investigated. LECs based on complex 1 emitted yellow electroluminescence (λ max 574nm) with Commission Internationale de L’Eclairage (CIE) coordinates of (0.49, 0.50) while the complex 2 gave yellowish-green electroluminescence (λ max 537nm) with CIE coordinates of (0.35, 0.58). The work done here reveals that the alkyl substituted phenanthroline ancillary ligand, tmphen shifts the light emission to the shorter wavelength region than the phenyl substituted dpphen ligand, resulting in the color tuning of the light-emitting devices. Density functional theory (DFT) calculations were performed to gain insight into the molecular surfaces of cationic iridium complexes and their electrochemical behaviors. Single layer LECs based on these complexes exhibited a high luminescence of 5199 and 4751cd/m2 for complexes 1 and 2 respectively. The ionic liquid, 1-ethyl-3-methylimidazolium hexafluorophosphate (EMIMPF6) was added to the light emitting layer and hence higher luminances were obtained than the pristine device. [Copyright &y& Elsevier]

Abstract: A novel blue-green light-emitting cationic iridium complex [Ir(ppz)2pzpy]PF6 (complex 1), where ppz is phenylpyrazole and pzpy is 2-(1-phenyl-1H-pyrazol-3-yl)pyridine, is developed. Its crystal, photophysical and electrochemical properties are characterized through experiments and quantum chemical calculations. The novel complex exhibits enlarged energy gap and blue-shifted emission spectrum at 77K compared to a reference complex, [Ir(ppy)2pzpy]PF6 (complex 2), with phenylpyridine (ppy) as the cyclometalated ligands. Moreover, light-emitting electrochemical cells (LECs) fabricated with complex 1 show both improved color purity with CIE (Commission Internationale de L’Eclairage) coordinates of (0.25, 0.39) and elongated lifespan (t 1/2 =218min, E tot =0.55mJ) compared to LECs based on complex 2. [Copyright &y& Elsevier]

Thiophene based polymers and oligomers have attracted considerable attention because they can be functionalized to alter the gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), which enables the design of tunable light emitting materials. One area, which has been less explored, is the incorporation of low coordinate, low oxidation state main group elements into these systems. We have currently developed a novel p-conjugated ligand containing two contiguous thiophene rings in which we have demonstrated its ability to support both pnictogen cations and their metal complexes. [ABSTRACT FROM AUTHOR]

A new cationic iridium complex has been developed with 2-(1-phenyl-1H-pyrazol-3-yl)pyridine as the ancillary ligand, which bears a pendant protective phenyl ring within the molecule; blue-green light-emitting electrochemical cells (LECs) based on the complex show dramatically enhanced stability compared to the LEC based on a similar complex without pendant phenyl rings. [ABSTRACT FROM AUTHOR]