High Phosphorescence Efficiency Research Articles

Recent Advances in Room-Temperature Phosphorescence Metal-Organic Hybrids: Structures, Properties, and Applications.

Metal-organic hybrid (MOH) materials with room-temperature phosphorescence (RTP) have drawn attention in recent years due to their superior RTP properties of high phosphorescence efficiency and ultralong emission lifetime. Great achievement has been realized in developing MOH materials with high-performance RTP, but a systematic study on MOH materials with RTP feature is lacking. This review highlights recent advances in metal-organic hybrid RTP materials. The molecular packing, the photophysical properties, and their applications of metal-organic hybrid RTP materials are discussed in detail. Metal-organic hybrid RTP materials can be divided into six parts: coordination polymers, metal-organic frameworks (MOFs), metal-halide hybrids, organic ionic crystals, organic ionic polymers, and organic-inorganic hybrid perovskites. These RTP materials have been successfully applied in time-resolved data encryption, fingerprint recognition, information logic gates, X-ray imaging, and photomemory. This review not only provides the basic principles of designing RTP metal-organic hybrids, but also propounds the future research prospects of RTP metal-organic hybrids. This review offers many effective strategies for developing metal-organic hybrids with excellent RTP properties, thus satisfying practical applications.

Ultralong afterglow of heavy-atom-free carbon dots with a phosphorescence lifetime of up to 3.7 s for encryption and fingerprinting description.

Metal-free room-temperature phosphorescent (RTP) materials with changeable colors have attracted great attention in anti-counterfeiting information encryption. Most ultralong-lifetime RTP (URTP) luminophores are traditionally obtained through heavy atom effects via enhancing the spin-orbit coupling efficiency. Here, we report the self-assembly of URTP carbon dots (CDs) using diphenylaminourea as the precursor through a thermal-evaporation assisted covalent-binding approach in the presence of boric acid (BA). The BA-functionalized diphenylaminourea-derived CDs (denoted as D-CDs1.5/BA composites) show a rigid network structure with B-C linkages connected to the surface of the CDs, which can effectively suppress the free vibration of CDs to promote intersystem crossover, finally resulting in an excellent URTP afterglow performance. They feature a low singlet-triplet energy gap and reduced nonradiative attenuation properties. As a result, the D-CDs1.5/BA composites exhibit a bifunctional fluorescence/phosphorescence performance with a high phosphorescence quantum efficiency (12.67%) and an ultra-long green afterglow phosphorescence lifetime of up to 3.66 s. A high-level information encryption and fingerprinting description based on the URTP D-CDs1.5/BA composites were then investigated. This work contributes to the feasible design and preparation of novel URTP CD materials with both ultra-long afterglow and a high phosphorescence efficiency, making them promising candidates for advanced anti-counterfeiting applications.

High Intrinsic Phosphorescence Efficiency and Density Functional Theory Modeling of Ru(II)-Bipyridine Complexes with π-Aromatic-Rich Cyclometalated Ligands: Attributions of Spin-Orbit Coupling Perturbation and Efficient Configurational Mixing of Singlet Excited States.

A series of π-aromatic-rich cyclometalated ruthenium(II)-(2,2'-bipyridine) complexes ([Ru(bpy)2(πAr-CM)]+) in which πAr-CM is diphenylpyrazine or 1-phenylisoquinoline were prepared. The [Ru(bpy)2(πAr-CM)]+ complexes had remarkably high phosphorescence rate constants, k RAD(p), and the intrinsic phosphorescence efficiencies (ιem(p) = k RAD(p)/(νem(p))3) of these complexes were found to be twice the magnitudes of simply constructed cyclometalated ruthenium(II) complexes ([Ru(bpy)2(sc-CM)]+), where νem(p) is the phosphorescence frequency and sc-CM is 2-phenylpyridine, benzo[h]quinoline, or 2-phenylpyrimidine. Density functional theory (DFT) modeling of the [Ru(bpy)2(CM)]+ complexes indicated numerous singlet metal-to-ligand charge transfers for 1MLCT-(Ru-bpy) and 1MLCT-(Ru-CM), excited states in the low-energy absorption band and 1ππ*-(aromatic ligand) (1ππ*-LAr) excited states in the high-energy band. DFT modeling of these complexes also indicated phosphorescence-emitting state (Te) configurations with primary MLCT-(Ru-bpy) characteristics. The variation in ιem(p) for the spin-forbidden Te (3MLCT-(Ru-bpy)) excited state of the complex system that was examined in this study can be understood through the spin-orbit coupling (SOC)-mediated sum of intensity stealing (∑SOCM-IS) contribution from the primary intensity of the low-energy 1MLCT states and second-order intensity perturbation from the significant configuration between the low-energy 1MLCT and high-energy intense 1ππ*-LAr states. In addition, the observation of unusually high ιem(p) magnitudes for these [Ru(bpy)2(πAr-CM)]+ complexes can be attributed to the values for both intensity factors in the ∑SOCM-IS formalism being individually greater than those for [Ru(bpy)2(sc-CM)]+ ions.

A Benzene Ring‐Linked Dimethylamino and Borate Ester‐Based Molecule and Organic Crystal: Efficient Dual Room‐Temperature Phosphorescence with Responsive Property

AbstractPure organic crystal of N,N‐di‐methyl‐4‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)aniline (DMAB) exhibits efficient room‐temperature phosphorescence (RTP) with an emission maximum at 387 nm and a high phosphorescence efficiency of 35.2%. Significantly, DMAB shows an exceptional photo‐induced ultra‐long RTP (URTP) at 539 nm, which displays an afterglow time of 14 s in air. The two phosphorescent bands are attributed to the monomeric and aggregated RTP of DMAB, respectively. Continuous UV irradiation for ≈1 min can dramatically improve the lifetimes for both of the monomeric and aggregated phosphorescent emissions. The photo‐induced URTP can be spontaneously switched off after standing the crystal in air for 50 min, and this cyclic process has been repeated several times. The molecular packing based on multiple intermolecular noncovalent interactions is adopted in DMAB crystal, which is beneficial to RTP. Upon UV irradiation, the consumption of oxygen in the crystal matrix accounts for the distinctive photo‐induced URTP. Taking advantage of the unique photo/oxygen‐sensitive properties, DMAB crystals have been successfully utilized in oxygen sensing and anticounterfeiting.

Cationic Ir(III) Complexes Featuring Phenylimidazole-type Cyclometalated Ligands: Fluorine-Free Blue Phosphorescent Emitters for Light-Emitting Devices.

The development of blue emissive cationic Ir(III) complexes with no fluorine substitutions but with sufficient blue color purity and high phosphorescence efficiency has remained challenging. Here, fluorine-free cyan to deep blue emissive cationic Ir(III) complexes with phenylimidazole-type cyclometalated ligands (C∧N) are reported, which are [Ir(dphim)2(dmapzpy)]PF6 (1), [Ir(ipr-dphim)2(dmapzpy)]PF6 (2), [Ir(ipr-dphim)2(bipz)]PF6 (3), and [Ir(ipr-dphim)2(bicb)]PF6 (4). 1,2-Diphenyl-1H-imidazole (dphim) and 1-(2,6-diisopropylphenyl)-2-phenyl-1H-imidazole (ipr-dphim) are the phenylimidazole-type C∧N ligands, and 4-dimethylamino-2-(1H-pyrazol-1-yl)pyridine (dmapzpy), di(1H-pyrazol-1-yl)methane (bipz), and 3,3'-methylenebis(1-methyl-1H-imidazol-3-ium-2-ide) (bicb) are the neutral ancillary ligands (A∧A). In both solution and diluted films, complex 1 shows a cyan emission with the emission maxima at ∼472 and 495 nm, and complexes 2-4 provide a deep blue emission with the emission maxima at ∼460 and 480 nm. While the complexes exhibit low to moderate phosphorescence efficiencies (0.05-0.35) in a degassed CH3CN solution, they exhibit high phosphorescence efficiencies (up to 0.82) in diluted films. Theoretical calculations revealed that the mixed 3π-π* (C∧N-centered)/3MLCT (Ir → C∧N) states are responsible for the emission afforded by complexes 1-4, which undergo nonradiative deactivations induced by different types of metal-centered states. Organic light-emitting diodes with complexes 1-4 as phosphorescent dopants are fabricated by a solution process, which affords a blue-green to blue emission with the emission maxima at ∼460 and 490 nm for the blue devices and a high current efficiency at 28.1 cd A-1 for the blue-green device. Solid-state light-emitting electrochemical cells are also fabricated with complexes 1-2 as phosphorescent dopants, which provide green-blue to blue emission with a high luminance (up to 840 cd m-2) and current-efficiency (up to 16.8 cd A-1) under a constant-current driving. The work reveals that, by using phenylimidazole-type C∧N ligands and optimized A∧A ligands, blue emissive cationic Ir(III) complexes with no fluorine substitutions but with sufficient blue-color purity and a high phosphorescence efficiency can be developed.

High Performance of Simple Organic Phosphorescence Host-Guest Materials and their Application in Time-Resolved Bioimaging.

The study of purely organic room-temperature phosphorescence (RTP) has drawn increasing attention because of its considerable theoretical research and practical application value. Currently, organic RTP materials with both high efficiency (ΦP > 20%) and a long lifetime (τP > 10 s) in air are still scarce due to the lack of related design guidance. Here, a new strategy to increase the phosphorescence performance of organic materials by integrating the RTP host and RTP guest in one doping system to form a triplet exciplex, is reported. With these materials, the high-contrast labeling of tumors in living mice and encrypted patterns in thermal printing are both successfully realized by taking advantage of both the long afterglow time (up to 25min in aqueous media) and high phosphorescence efficiency (43%).

Near-IR Charge-Transfer Emission at 77 K and Density Functional Theory Modeling of Ruthenium(II)-Dipyrrinato Chromophores: High Phosphorescence Efficiency of the Emitting State Related to Spin-Orbit Coupling Mediation of Intensity from Numerous Low-Energy Singlet Excited States.

Efficient charge-transfer (CT) phosphorescence in the near-IR (NIR) spectral region is reported for four substituted Ru-(R-dipyrrinato) complexes, [Ru(bpy)2(R-dipy)](PF6), where bpy is 2,2'-bipyridine and the substituent R is phenyl (ph), 2,4,6-trimethylphenyl, 4-carboxyphenyl (HOOC-ph), or 4-pyridinyl. The experimentally determined phosphorescence efficiency, ιem(p) = kRAD(p)/(νem(p))3 (where kRAD(p) and νem(p) are the phosphorescence rate constant and the phosphorescence frequency, respectively), of the [Ru(bpy)2(R-dipy)]+ complexes was approximately double that of [Ru(bpy)(Am)4]2+ complexes (Am = ammine ligand) in the NIR region. Density functional theory (DFT) modeling indicated two strikingly different electronic configurations of the triplet emitting state (Te) in the two types of complexes. The Te of [Ru(bpy)2(R-dipy)]+ complexes shows a CT-type corresponding to the metal-to-ligand charge transfer (MLCT)-(Ru-(R-dipy)) and the ππ*-(R-dipy) moiety configurations, and the Te state in the [Ru(bpy)(Am)4]2+ complexes corresponds to an approximately MLCT excited state consisting of mostly MLCT-(Ru-bpy) with a minimal ππ*(bpy) contribution. DFT modeling also indicated that the low-energy singlet excited states in the Te geometry (Sn(T)) of the [Ru(bpy)2(ph-dipy)]+ complex consist of numerous CT-Sn(T)-type states of the Ru-dipy and Ru-bpy moieties, whereas the [Ru(bpy)(Am)4]2+ ions show quite simple MLCT-Sn(T)-type states of the Ru-bpy moiety. Based on experimental observations, DFT modeling, and the plain spin-orbit coupling (SOC) principle, we conclude that the remarkably high ιem(p) amplitudes of the [Ru(bpy)2(R-dipy)]+ complexes relative to those of [Ru(bpy)(Am)4]2+ complexes can be attributed to the relatively substantial contribution of intrinsic SOC-mediated intensity stealing from the numerous low-energy CT-type Sn(T) states.

Multidimensional Structure Conformation of Persulfurated Benzene for Highly Efficient Phosphorescence.

It is a challenge to acquire, realize, and comprehend highly emissive phosphorescent molecules. Herein, we report that, using persulfurated benzene compounds as models, phosphorescence can be strongly enhanced through the modification of molecular conformation and crystal growth conditions. By varying the peripheral groups in these compounds, we were able to control their molecular conformation and crystal growth mode, leading to one- (1D), two- (2D), and three-dimensional (3D) crystal morphologies. Two kinds of typical molecular conformations were separately obtained in these crystals through substituent group control or the solvent effect. Importantly, a symmetrical 3,3-conformer exhibits that a planar central benzene ring prefers a 3D-type crystal growth mode, demonstrating high phosphorescence efficiency. Such outcome is attributed to the strong crystal protection effect of the 3D crystal and the bright global minimum (GM) boat-like T1 state of the symmetrical 3,3-conformer. The conformation studies further reveal small deformation of the inner benzene ring in both singlet and triplet states. The GM boat-like T1 state is indicated by theoretical calculations, which is far away from the conical intersection (CI) point between the S0 and T1 potential energy surfaces. Meanwhile, the small energy gap between S1 and T1 states and the considerable spin-orbit coupling matrix elements allow an efficient population of the T1 state. Combined with the crystal protection and conformation effect, the 3,3-conformer crystal shows high phosphorescence efficiency. The unsymmetrical 2,4-conformer conformation with the twisted central benzene ring leads to 1D or 2D crystal growth mode, which has a weak crystal protection effect. In addition, the unsymmetrical conformation has a dark GM T1 state that is very close to the T1-S0 CI point, implying an efficient nonradiative T1-S0 quenching. Thus, weak phosphorescence was observed from the unsymmetrical conformation. This study provides an insight for the development of highly emissive phosphorescent materials.

Molecular Engineering through Control of Structural Deformation for Highly Efficient Ultralong Organic Phosphorescence.

It is an enormous challenge to achieve highly efficient organic room-temperature phosphorescence (RTP) with a long lifetime. We demonstrate that, by bridging the carbazole and halogenated phenyl ring with a methylene linker, RTP phosphors CzBX (X=Cl, Br) present high phosphorescence efficiency (ΦPh ). A ΦPh up to 38 % was obtained for CzBBr with a lifetime of 220 ms, which is much higher than that of compounds CzPX (X=Cl, Br) with a C-N bond as a linker (ΦPh <1 %). Single-crystal analysis and theoretical calculations revealed that, in the crystal phase, intermolecular π-Br interactions accelerate the intersystem crossing process, while tetrahedron-like structures induced by sp3 methylene linkers restrain the nonradiative decay channel, leading to the high phosphorescence efficiency in CzBBr. This research paves a new road toward highly efficient and long-lived RTP materials with potential applications in anti-counterfeiting or data encryption.

Molecular Engineering through Control of Structural Deformation for Highly Efficient Ultralong Organic Phosphorescence

AbstractIt is an enormous challenge to achieve highly efficient organic room‐temperature phosphorescence (RTP) with a long lifetime. We demonstrate that, by bridging the carbazole and halogenated phenyl ring with a methylene linker, RTP phosphors CzBX (X=Cl, Br) present high phosphorescence efficiency (ΦPh). A ΦPh up to 38 % was obtained for CzBBr with a lifetime of 220 ms, which is much higher than that of compounds CzPX (X=Cl, Br) with a C−N bond as a linker (ΦPh&lt;1 %). Single‐crystal analysis and theoretical calculations revealed that, in the crystal phase, intermolecular π‐Br interactions accelerate the intersystem crossing process, while tetrahedron‐like structures induced by sp3 methylene linkers restrain the nonradiative decay channel, leading to the high phosphorescence efficiency in CzBBr. This research paves a new road toward highly efficient and long‐lived RTP materials with potential applications in anti‐counterfeiting or data encryption.

Colour-tunable ultralong-lifetime room temperature phosphorescence with external heavy-atom effect in boron-doped carbon dots

• Boron-doped carbon dots (BDs) are prepared from citric acid and boric acid. • BDs possesses high PLQY (40.4%) and PQY (23.5%), together with long afterglow lifetime (1.17 s). • BD-X was obtained from citric acid, boric acid and KX (X = Cl, Br and I). • BD-X exhibits extraordinarily high PQY of 34.4% and untralong afterglow lifetime of 2.61 s. • BDs and BD-X are successfully employed for anti-counterfeiting and information encryption. Color-tunable ultralong-lifetime room temperature phosphorescence (URTP) materials have become powerful candidates for the extensive applications of optoelectronics, information encryption, anti-counterfeiting and sensing. Nevertheless, it hard to prepare URTP luminophores with both long afterglow lifetime and high phosphorescence quantum yield (PQY) under ambient conditions. Herein, we developed a convenient, rapid and gram-scale method to successfully obtain a series of URTP boron-doped carbon dots (BDs, named as BD50, BD100, BD150 and BD300, respectively), utilizing boric acid (BA, 3 g) and citric acid (CA, 50, 100, 150 and 300 mg) as precursers. BD50 shows prominent multi-colour emissive photoluminescence (PL) and phosphorescence, with extraordinarily high PL quantum yield (PLQY, 40.4%) and PQY (23.5%). Moreover, BD50 exhibits bright yellow-green afterglow, with lifetime as high as 1.17 s. What worth more to joy and encourage is that significant improvements in PQY and lifetime were achieved by introducing halide ions into BDs, due to external heavy-atom effect (EHE). BD-X (X = Cl, Br and I) possesses high PQY and long lifetime (up to 34.4% and 2.61 s). Based on the unique RTP performance of BDs and BD-X, these URTP luminophores are successfully applied to anti-counterfeiting and information encryption. This work contributes to develop smart materials with ultralong afterglow and high phosphorescence efficiency.

A Highly Efficient Red Metal-free Organic Phosphor for Time-Resolved Luminescence Imaging and Photodynamic Therapy.

Developing highly efficient red metal-free organic phosphors for biological applications is a formidable challenge. Here, we report a novel molecular design principle to obtain red metal-free organic phosphors with long emission lifetime (504.6 μs) and high phosphorescence efficiency (14.6%) from the isolated molecules in the crystal. Furthermore, the well-dispersed phosphorescent nanodots (PNDs) with the particle size around 5 nm are prepared through polymer-encapsulation in an aqueous solution, which show good biocompatibility and low cytotoxicity. The metal-free PNDs are successfully applied to time-resolved luminescence imaging to eliminate background fluorescence interference both invitro and vivo as well as effective photodynamic anticancer therapy for the first time. This work will not only pave a pathway to develop highly efficient metal-free RTP materials but also expand the scope of their applications to biomedical fields.

Photophysical and optoelectronic properties of a platinum(II) complex and its derivatives, designed as a highly efficient OLED emitter: A theoretical study

AbstractNew platinum(II) complex with picolinate (pic) and 2‐phenyl naphtothiazole (pntl) ligand as the guest material has been designed and its capability for OLED applications have been examined. Also, we have studied the effects of different substitutions (ie, electron‐withdrawing and electron donating groups) on naphtothiazole moiety on optovoltaic characters. We have employed density functional theoretical (B3LYP/DFT) methods to reveal the photophysical and structure properties relationships with the typical host material. The valence MO energies, vertical and adiabatic triplet energy, reorganization energy, and triplet exciton generation fraction (χ T) have been extensively studied to exploring high phosphorescence efficiency in OLEDs. It has been predicted that substituted systems are good candidates for OLED applications as well as their parent system.

A theoretical investigation on the neutral Cu(I) phosphorescent complexes with azole-based and phosphine mixed ligand

ABSTRACTA theoretical study on a series of neutral heteroleptic Cu(I) complexes with different azole-pyridine-based N^N ligands has been presented to get insight into the effect of various nitrogen atoms in the azole ring on photophysical properties. The results reveal that the highest occupied molecular orbital (HOMO) levels and the emission wavelengths of these complexes are mainly governed by the nitrogen atom number in azole ring. With the increasing number of nitrogen atom , the electron density distribution of HOMO gradually extend from the N^N ligand to the whole molecule, meanwhile, the improved contribution from Cu(d) orbits in HOMO results in an effective mixing of various charge transfermodes, and hence, the fast radiative decay(kr) and the slow non-radiative decay rate(knr) are achieved. The photoluminescence quantum yield (PLQY) show an apparent dependence on the nitrogen atom number in the five-membered nitrogen heterocycles. However, the increasing number of nitrogen atoms is not necessary for increasing PLQY. The complex 3 with 1,2,4-triazole-pyridine-based N^N ligands is considered to be a potential emitter with high phosphorescence efficiency. Finally, we hope that our investigations will contribute to systematical understanding and guiding for material molecular engineering.

Visible-Light-Excited Ultralong Organic Phosphorescence by Manipulating Intermolecular Interactions.

Visible light is much more available and less harmful than ultraviolet light, but ultralong organic phosphorescence (UOP) with visible-light excitation remains a formidable challenge. Here, a concise chemical approach is provided to obtain bright UOP by tuning the molecular packing in the solid state under irradiation of available visible light, e.g., a cell phone flashlight under ambient conditions (room temperature and in air). The excitation spectra exhibit an obvious redshift via the incorporation of halogen atoms to tune intermolecular interactions. UOP is achieved through H-aggregation to stabilize the excited triplet state, with a high phosphorescence efficiency of 8.3% and a considerably long lifetime of 0.84 s. Within a brightness of 0.32 mcd m-2 that can be recognized by the naked eye, UOP can last for 104 s in total. Given these features, ultralong organic phosphorescent materials are used to successfully realize dual data encryption and decryption. Moreover, well-dispersed UOP nanoparticles are prepared by polymer-matrix encapsulation in an aqueous solution, and their applications in bioimaging are tentatively being studied. This result will pave the way toward expanding metal-free organic phosphorescent materials and their applications.

Manipulation of phosphorescence efficiency of cyclometalated iridium complexes by substituted o-carboranes.

A series of [(C^N)2 Ir(acac)] complexes [{5-(2-R-CB)ppy}2 Ir(acac)] (3 a-3 g; acac=acetylacetonate, CB=o-carboran-1-yl, ppy=2-phenylpyridine; R=H (3 a), Me (3 b), iPr (3 c), iBu (3 d), Ph (3 e), CF3 C6 H4 (3 f), C6 F5 (3 g)) with various 2-R-substituted o-carboranes at the 5-position in the phenyl ring of the ppy ligand were prepared. X-ray diffraction studies revealed that the carboranyl CC bond length increases with increasing steric and electron-withdrawing effects from the 2-R substituents. Although the absorption and emission wavelengths of the complexes are almost invariant to the change of 2-R group, the phosphorescence quantum efficiency varies from highly emissive (ΦPL ≈0.80 for R=H, alkyl) to poorly emissive (R=aryl) depending on the 2-R group and the polarity of the medium. Theoretical studies suggest that 1) the almost nonemissive nature of the 2-aryl-substituted complexes is mainly attributable to the large contribution to the LUMO in the S1 excited state from an o-carborane unit and 2) the variation in the CC bond length between the S0 and T1 state structures increases with increasing steric (2-alkyl) and electronic effects (2-aryl) of the 2-R substituent and the polarity of the solvent. The solution-processed electroluminescence (EL) devices that incorporated 3 b and 3 d as emitters displayed higher performance than the device based on the parent [(ppy)2 Ir(acac)] complex. Along with the high phosphorescence efficiency, the bulkiness of the 2-R-o-carborane unit is shown to play an important role in improving device performance.

A theoretical study on supramolecularly-caged positively charged iridium(iii) 2-pyridyl azolate derivatives as blue emitters for light-emitting electrochemical cells

The photophysical and optical properties of a series of charged biscyclometalated [Ir(ppy(n))2(N^N(n))](+) complexes have been investigated with density functional theory, where ppy(0) = 2-phenylpyridine; ppy(1) = 2-(2,4-difluorophenyl)pyridine; N^N = 2-(1-phenyl-1H-pyrazol-3-yl)pyridine (1a, 1b); 2-(4-phenyl-1H-imidazol-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 (Φ(PL)) of 23% and 20% compared with 1a with Φ(PL) of 3%. To clarify this behavior, the metal-to-ligand charge transfer contributions (MLCT%), the S1-T1 splitting energy (ΔE(S1-T1)) and the transition dipole moment (μ(S1)) upon the S0→S1 transition were calculated. Drastically small ΔE(S1-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 Φ(PL) observed experimentally. Besides, the remarkably small ΔE(S1-T1), large MLCT% and similar μ(S1) 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.

Theoretical Study on Cationic Iridium(III) Complexes with a Diphosphane Ligand – Geometry, Electronic Properties, and Application for Light‐Emitting Electrochemical Cells

AbstractA DFT/time‐dependent DFT (TD‐DFT) investigation was conducted on a series of cationic iridium(III) complexes with 2‐phenylpyridine (ppyn) derivatives and a diphosphane (PPn) ancillary ligand to shed light on the effects of stereoisomerism and ligand substituents on the photophysical properties. The geometries, electronic structures, lowest‐lying singlet–singlet absorptions, vertical singlet–triplet excitations, and triplet–singlet emissions of N,N‐cis‐[Ir(ppy0)2(PP)]+ (1), N,N‐trans‐[Ir(ppy0)2(PP)]+ (2) and their derivatives were investigated with DFT‐based approaches [ppy0 = 2‐phenylpyridine, PP = 1,2‐bis(diphenylphosphanyl)ethene]. The complex N,N‐trans‐[Ir(ppy2)2(PP2)]+ (3b) shows high quantum phosphorescence efficiency (ΦPL) of 91 %, whereas an extremely low ΦPL (&lt;1 %) was observed for N,N‐trans‐[Ir(ppy4)2(PP1)]+ (2d). To clarify this behavior, the S1–Tn splitting energy (ΔE), the transition dipole moment (μ) upon the S0→S1 transition, and the energy gap between the triplet metal‐to‐ligand charge transfer (3MLCT) π–π* and triplet metal‐centered (3MC) d–d states (ΔEMC–MLCT) were calculated. A drastically small ΔE and large μ for 3b (&lt;0.05 eV and 1.38 D, respectively), compared to those for 2d (&gt;0.2 eV and 1.26 D, respectively), were found to be closely linked to the substituents on the ppyn ligands. The remarkably small ΔE and similar μ for N,N‐cis 1c (&lt;0.05 eV and 1.41 D, respectively), compared to those for N,N‐trans 2c (&gt;0.1 eV and 1.42 D, respectively), could be attributed to the effects of the trans–cis structural isomerism. On the basis of these parameters, the higher ΦPL of 3b with respect to that of 2d was explained, and 1c, 1d, 2b, and 2e were considered to have better physical properties than the experimentally synthesized complexes 2, 2d, and 3b. The newly designed 1c, 1d, 2b, and 2e are expected to be highly emissive in the blue‐green region for light‐emitting electrochemical cell (LEC) applications.

Phosphorescent iridium(iii) complexes: toward high phosphorescence quantum efficiency through ligand control

Phosphorescent Ir(III) complexes attract enormous attention because they allow highly efficient electrophosphorescence. In pursuing the development of Ir(III) complexes during the last decade, significant progress has been made in terms of the colour-tunability, thermal- and photo-stability, phase homogeneity, and phosphorescence efficiency. By far, extensive synthetic efforts have been focused on the molecular design of ligands to achieve a wide range of phosphorescence colour that is compatible with organic light-emitting device (OLED) applications. In contrast, less has been known about a collective structure-property relationship for phosphorescence quantum efficiency. In fact, a few rule-of-thumbs for high phosphorescence quantum efficiency have been occasionally reported, but a collective rationale is yet to be investigated. In this article, we provide a comprehensive review of 8 different methods reported so far to achieve high phosphorescence quantum efficiency from Ir(III) complexes. The methods included herein are limited to the cases of intramolecular controls, and thus are discussed in terms of variations in ligand structures: (1) geometric isomer control, (2) rigid structure and restricted intramolecular motion, (3) larger mixing of 1MLCT and 3LC states, (4) de-stabilizing a thermally accessible non-emissive state, (5) introducing dendrimer structures, (6) control in substituents of ligands, (7) confining the phosphorescent region of a mixed ligand Ir(III) complex and (8) sensitized phosphorescence by using attached energy donors. Each method is closely related to intramolecular excited state interactions, which strongly affect radiative or non-radiative transitions. A comprehensive understanding of these methods leads us to conclude that the modulation in ligand structures has a profound effect on both the phosphorescence colour and phosphorescence quantum efficiency. Thus, the judicious selection of ligand structures and their chelate disposition should be considered before synthesis. We expect that the guidelines for attaining a high phosphorescence efficiency, summarized in this Perspective, would be helpful in developing highly phosphorescent Ir(III) complexes.

Efficient blue-green organic light-emitting diodes based on heteroleptic tris-cyclometalated iridium(III) complexes

The blue-green organic light-emitting diodes based on heteroleptic tris-cyclometalated iridium(III) complexes containing the F 2-ppy (2,4-difluorophenylpyridine) and ppy (2-phenylpyridine) ligands were fabricated. Ir(ppy) 3 has been known to have a high phosphorescence efficiency in electroluminescence owing to its strong metal-to-ligand-charge transfer (MLCT) excited state, whereas the luminous efficiency of Ir(F 2-ppy) 3 was found to be low due to weak MLCT. Herein, we report two heteroleptic phosphorescent blue-green emitters, Ir(ppy) 2(F 2-ppy) and Ir(ppy)(F 2-ppy) 2, that exhibit emission peaks at 502 nm and 495 nm, respectively. The maximum luminous efficiencies of the devices with Ir(ppy) 2(F 2-ppy) and Ir(ppy)(F 2-ppy) 2 were 8.93 cd/A and 13.80 cd/A, respectively. The quantum efficiency of the device containing Ir(ppy)(F 2-ppy) 2 was 3.63% at J = 10 mA/cm 2.