Effects of Deuterium Isotopes on Pt(II) Complexes and Their Impact on Organic NIR Emitters.

Insight into effect of deuterium isotopes on organic near-IR (NIR) emitters was explored by the use of self-assembled Pt(II) complexes H-3-f and HPh-3-f, and their deuterated analogues D-3-f and DPh-3-f, respectively (Scheme 2). In vacuum deposited thin film, albeit having nearly identical emission spectral feature maximized at ~810 nm, H-3-f and D-3-f exhibit remarkable difference in photoluminescence quantum yield (PLQY) of 29 % and 50 %, respectively. Distinction in PLQY is also observed for HPh-3-f (800 nm, 50 %) and DPh-3-f (798 nm, 67 %). We then elucidated the theoretical differences in the impact on near-infrared (NIR) luminescence between Pt(II) complexes and organic small molecules upon deuteration. The results establish a general guideline for the deuteration on NIR emission efficiency. From a perspective of practical application, NIR OLEDs based on D-3-f and DPh-3-f emitters attain EQEmax of 15.5 % (radiance 31,287 mW Sr-1 m-2 ) and 16.6 % (radiance of 32,279 mW Sr-1 m-2 ) at 764 nm and 796 nm, respectively, both of which set new records for NIR OLEDs of >750 nm.

Exciplex-Forming Cohost Systems with 2,3-Dicyanopyrazinophenanthrene-based Acceptors to Achieve Efficient Near Infrared OLEDs.

Two new 2,3-dicyanopyrazinophenanthrene-based acceptors (A) p-QCN and m-QCN were synthesized to blend with a donor (D) CPTBF for the exciplex formation. The energy levels of p-QCN and m-QCN are modulated by the peripheral substituents 4- and 3-benzonitrile, respectively. Exciplex-forming blends were identified by the observation of the red-shifted emissions from various D : A blends with higher ratios of donor for suppressing the aggregation of acceptor. The two-component relaxation processes observed by time-resolved photoluminescence support the thermally activated delayed fluorescence (TADF) character of the exciplex-forming blends. The device employing CPTBF : p-QCN and (2 : 1) and CPTBF : m-QCN (2 : 1) blend as the emitting layer (EML) gave EQEmax of 1.76 % and 5.12 %, and electroluminescence (EL) λmax of 629 nm and 618 nm, respectively. The device efficiency can be further improved to 4.32 % and 5.57 % with CPTBF : p-QCN and (4 : 1) and CPTBF : m-QCN (4 : 1) as the EML, which is consistent with their improved photoluminescence quantum yields (PLQYs). A new fluorescent emitter BPBBT with photoluminescence (PL) λmax of 726 nm and a high PLQY of 67 % was synthesized and utilized as the dopant of CPTBF : m-QCN (4 : 1) cohost system. The device employing CPTBF : m-QCN (4 : 1): 5 wt.% BPBBT as the EML gave an EQEmax of 5.02 % and EL λmax centered at 735 nm, however, the weak residual exciplex emission remains. By reducing the donor ratio, the exciplex emission can be completely transferred to BPBBT and the corresponding device with CPTBF : m-QCN (2 : 1): 5 wt.% BPBBT as the EML can achieve EL λmax of 743 nm and EQEmax of 4.79 %. This work manifests the high efficiency near infrared (NIR) OLED can be realized by triplet excitons harvesting of exciplex-forming cohost system, followed by the effective energy transfer to an NIR fluorescent dopant.

A Survey of the Regulatory Requirements for the Waiver of In Vivo Bioequivalence Studies of Generic Products in Certain Dosage Forms by Participating Regulators and Organisations of the International Pharmaceutical Regulators Programme.

The requirements to waive in vivo bioequivalence studies for immediate release solid oral dosage forms based on the Biopharmaceutics Classifications System (BCS) are well known, and biowaivers[1] for other types of oral dosage forms based on pre-defined criteria may also be acceptable. Similarly, biowaivers for dosage forms such as injectable products may also be allowed if certain criteria are met. The current paper summarises the biowaiver requirements for oral solutions and suspensions, soft gelatin capsules and injectable products (intravenous injections, subcutaneous and intramuscular injections, emulsions for injection and micellar solutions for injection) among the participants of the Bioequivalence Working Group for Generics (BEWGG) of the International Pharmaceutical Regulators Programme (IPRP). A review of the requirements indicated that there was a trend towards convergence when the dosage form became less complex; however, the most common approach used by each of the jurisdictions was a case-by-case approach given that most jurisdictions do not have well defined guidelines to support all possible scenarios. Even in the simplest case of intravenous solutions, the acceptability of qualitative changes in excipients differ between the IPRP members.  Notwithstanding the differences, the dissemination of the information is a first step towards regulatory convergence regarding biowaivers for certain dosage forms and should be useful for pharmaceutical companies currently developing generic medicinal products for IPRP jurisdictions.

Requirements for Additional Strength Biowaivers for Modified Release Solid Oral Dosage Forms in International Pharmaceutical Regulators Programme Participating Regulators and Organisations: Differences and Commonalities.

This article describes an overview of waivers of in vivo bioequivalence studies for additional strengths in the context of the registration of modified release generic products and is a follow-up to the recent publication for the immediate release solid oral dosage forms. The current paper is based on a survey among the participating members of the Bioequivalence Working Group for Generics (BEWGG) of the International Pharmaceutical Regulators Program (IPRP) regarding this topic. Most jurisdictions consider the extrapolation of bioequivalence results obtained with one (most sensitive) strength of a product series as less straightforward for modified release products than for immediate release products. There is consensus that modified release products should demonstrate bioequivalence not only in the fasted state but also in the fed state, but differences exist regarding the necessity of additional multiple dose studies. Fundamental differences between jurisdictions are revealed regarding requirements on the quantitative composition of different strengths and the differentiation of single and multiple unit dosage forms. Differences in terms of in vitro dissolution requirements are obvious, though these are mostly related to possible additional comparative investigations rather than regarding the need for product-specific methods. As with the requirements for immediate release products, harmonization of the various regulations for modified release products is highly desirable to conduct the appropriate studies from a scientific point of view, thus ensuring therapeutic equivalence.

The Requirements for Additional Strength Biowaivers for Immediate Release Solid Oral Dosage Forms in International Pharmaceutical Regulators Programme Participating Regulators and Organisations: Differences and Commonalities.

In relation to the registration of generic products, waivers of in vivo bioequivalence studies (biowaivers) are considered in three main cases: certain dosage forms for which bioequivalence is self-evident (e.g. intravenous solutions), biowaivers based on the Biopharmaceutics Classification System and biowaivers for additional strengths with respect to the strength for which in vivo bioequivalence has been shown. The objective of this article is to describe the differences and commonalities in biowaivers for additional strengths of immediate release solid oral dosage forms between the participating members of the International Pharmaceutical Regulators Program (IPRP). The requirements are based on five main aspects; the pharmacokinetics of the drug substance, the manufacturing process, the qualitative and quantitative composition of the different strengths, and the comparative dissolution profiles. For the pharmacokinetic aspects, many regulators/agencies have the same requirements. All strengths must be manufactured with the same process, although a few regulators/agencies accept small differences. In relation to the formulation aspects, the data required breaks down into three major approaches based initially on one of those of the EU, the USA or Japan, but there are some differences in these three major approaches with some country specific interpretations. Most regulators/agencies also have the same requirements for the dissolution data, though there are some notable exceptions.

A Survey of the Regulatory Requirements for the Acceptance of Foreign Comparator Products by Participating Regulators and Organizations of the International Generic Drug Regulators Programme.

The acceptance of foreign comparator products is the most limiting factor for the development and regulatory assessment of generic medicines marketed globally. Bioequivalence studies have to be repeated with the local comparator products of each jurisdiction because it is unknown if the comparators of the different countries are the same product, with the consequent duplication of efforts by regulators and industry alike. The regulatory requirements on the acceptability of foreign comparator products of oral dosage forms differ between countries participating in the Bioequivalence Working Group for Generics of the International Pharmaceutical Regulators Programme. Brazil, Colombia, the European Union member States, Japan, Mexico, South Korea and the United States only accept bioequivalence studies with their local comparator. In contrast, Australia, Canada, New Zealand, Singapore, South Africa, Switzerland and Taiwan accept studies with foreign comparators under certain conditions. Canada limits its use to highly soluble drugs with a wide therapeutic range in immediate release products. Australia requires a comparison of the quantitative composition. In contrast, there are fewer restrictions on the acceptance of foreign comparators in New Zealand, Singapore, South Africa, Switzerland and Taiwan. For the WHO Prequalification of Medicines and for developing generics of the essential medicines the WHO lists comparators from different countries. In conclusion, there is currently no consensus amongst regulators on the acceptability of foreign comparator products.

A Survey of the Regulatory Requirements for BCS-Based Biowaivers for Solid Oral Dosage Forms by Participating Regulators and Organisations of the International Generic Drug Regulators Programme.

PURPOSE: The Biopharmaceutics Classification System (BCS) based biowaiver is a scientific model which enables the substitution of in vivo bioequivalence studies with in vitro data as evidence of therapeutic equivalence subject to certain conditions. Despite being based on the same principles, BCS-based biowaivers are interpreted and regulated differently among international regulatory agencies. In this survey, the Bioequivalence Working Group (BEWG) of the International Generic Drug Regulators Programme (IGDRP) compared the criteria for BCS-based biowaivers applied by the participating regulators and organisations. METHODS: Differences and similarities regarding solubility, permeability, dissolution, excipients and fixed-dose combination products, were identified and compared in a detailed survey of each participant's criteria for BCS-based biowaivers. These criteria were determined based upon the participants' respective regulatory guidance documents, policies and practices. RESULTS: This review has, with the exception of two participants who do not accept BCS-based biowaivers, revealed that most IGDRP participants interpret the BCS principles and conditions similarly but notable differences exist in the application of these principles.  Conclusion: Although many similarities exist, this review identifies several opportunities for greater convergence of regulatory requirements amongst the surveyed jurisdictions. This article is open to POST-PUBLICATION REVIEW. Registered readers (see "For Readers") may comment by clicking on ABSTRACT on the issue's contents page.

Sky Blue-Emitting Iridium(III) Complexes Bearing Nonplanar Tetradentate Chromophore and Bidentate Ancillary.

Tetradentate chelates bearing tripodal arranged terpyridine and a functional pyrazole unit (i.e., L1-H and L2-H) were employed in preparation of Ir(III) complexes [Ir(L1)Cl2] (1) and [Ir(L2)Cl2] (2); subsequent chloride-to-bipyrazolate substitution gave [Ir(L1)(bipz)] (3) and [Ir(L2)(bipz)] (4). Single-crystal X-ray structural studies on 1 and 3 showed the possession of a tetradentate chelate, whereas the remaining cis-sites are occupied by either dual chlorides or the bipz chelate, respectively. Sky blue organic light-emitting diode with peak efficiencies (10.1%, 19.8 cd·A-1, and 20.4 lm·W-1) was successfully fabricated using 3 (or 4) as dopant emitter, highlighting the potential application of this class of Ir(III) phosphor.

N-H-Type Excited-State Proton Transfer in Compounds Possessing a Seven-Membered-Ring Intramolecular Hydrogen Bond.

A series of compounds containing 5-(2-aminobenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one (o-ABDI) as the core chromophore with a seven-membered-ring N-H-type intramolecular hydrogen bond have been synthesized and characterized. The acidity of the N-H proton and thus the hydrogen-bond strength can be fine-tuned by replacing one of the amino hydrogen atoms by a substituent R, the acidity increasing with increasing electron-withdrawing strength of R, that is, in the order H

Pt(II) Phosphors Featuring Both Dicarbene and Functional Biazolate Chelates: Synthesis, Luminescent Properties, and Applications in Organic Light-Emitting Diodes.

Pt(II) metal complexes [Pt(C^C)(X^X)] comprising three functional dianionic azolate chelates (X^XH2: bipzH2 = 5,5'-di(trifluoromethyl)-3,3'-bipyrazole, bitzH2 = 5,5'-di(trifluoromethyl)-3,3'-bi-1,2,4-triazole, and phpzH2 = 3-(trifluoromethyl)-5-(4-(trifluoromethyl)phenyl)-1H-pyrazole), together with three different charge-neutral dicarbene chelates (i.e., C^C = 1,1'-methylene bis(3-methyl-imidazol-2-ylidene), 1,1'-methylene bis(3-isopropyl-imidazol-2-ylidene), and 1,1'-(propane-1,3-diyl) bis(3-isopropyl-imidazol-2-ylidene), were synthesized and found to show bright solid-state emission depending on the associated X^X and C^C chelates. Pt(II) complexes 1a, 2, and 6 were examined by X-ray diffraction studies, confirming the square-planar skeleton. These Pt(II) metal complexes are found to be nonemissive in degassed solution at RT. The photophysical measurements as neat powder reveals emission maxima ranging from purple to sky blue emission and with high quantum yields for the majority of them. (Time-dependent) density functional theory (DFT/TD-DFT) calculations were executed to elucidate the emission process that was predominated by the combined3LLCT/(3)LMCT/(3)IL character, where LLCT and LMCT and IL stand for ligand-to-ligand charge transfer, ligand-to-metal charge transfer, and intraligand ππ* transition processes. Organic light-emitting devices comprising complex 5a achieved high efficiency (8.9%, 19.4 cd·A(-1), 22.5 lm·W(-1)) with a sky blue emission showing CIEx,y coordinates of (0.18, 0.32).

Optically Triggered Stepwise Double-Proton Transfer in an Intramolecular Proton Relay: A Case Study of 1,8-Dihydroxy-2-naphthaldehyde.

1,8-Dihydroxy-2-naphthaldehyde (DHNA), having doubly intramolecular hydrogen bonds, was strategically designed and synthesized in an aim to probe a long-standing fundamental issue regarding synchronous versus asynchronous double-proton transfer in the excited state. In cyclohexane, DHNA shows the lowest lying S0 →S1 (π-π*) absorption at ∼400 nm. Upon excitation, two large Stokes shifted emission bands maximized at 520 and 650 nm are resolved, which are ascribed to the tautomer emission resulting from the first and second proton-transfer products, denoted by TA* and TB*, respectively. The first proton transfer (DHNA* → TA*) is ultrafast (< system response of 150 fs), whereas the second proton transfer is reversible, for which the rates of forward (TA* → TB*) and backward (TA* ← TB*) proton transfer were determined to be (1.7 ps)(-1) and (3.6 ps)(-1), respectively. The fast equilibrium leads to identical population lifetimes of ∼54 ps for both TA* and TB* tautomers. Similar excited-state double-proton transfer takes place for DHNA in a single crystal, resulting in TA* (560 nm) and TB* (650 nm) dual-tautomer emission. A comprehensive 2D plot of reaction potential energy surface further proves that the sequential two-step proton motion is along the minimum energetic pathway firmly supporting the experimental results. Using DHNA as a paradigm, we thus demonstrate unambiguously a stepwise, proton-relay type of intramolecular double-proton transfer reaction in the excited state, which should gain fundamental understanding of the multiple proton transfer reactions.

Locked ortho- and para-core chromophores of green fluorescent protein; dramatic emission enhancement via structural constraint.

We report the design strategy and synthesis of a structurally locked GFP core chromophore p-LHBDI, its ortho-derivative, o-LHBDI, and H2BDI possessing both para- and ortho-hydroxyl groups such that the inherent rotational motion of the titled compounds has been partially restricted. o-LHBDI possesses a doubly locked configuration, i.e., the seven-membered ring hydrogen bond and five-membered ring C(4-5-10-13-14) cyclization, from which the excited-state intramolecular proton transfer takes place, rendering a record high tautomer emission yield (0.18 in toluene) and the generation of amplified spontaneous emission. Compared with their unlocked counterparts, a substantial increase in the emission yield is also observed for p-LHBDI and H2BDI in anionic forms in water, and accordingly the structure versus luminescence relationship is fully discussed based on their chemistry and spectroscopy aspect. In solid, o-LHBDI exhibits an H-aggregate-like molecular packing, offers narrow-bandwidth emission, and has been successfully applied to fabricate a yellow organic light emitting diodes (λmax = 568 nm, ηext = 1.9%) with an emission full width at half-maximum as narrow as 70 nm.

Tetragold(I) complexes: solution isomerization and tunable solid-state luminescence.

In this study, a new family of tetranuclear gold(I) triphosphine derivatives bearing alkynyl and thiolate groups have been efficiently synthesized by treating the polymeric acetylides (AuC2R)n or a thiolate (AuSPh)n sequentially with the (a) phosphine ligand and (b) cationic complex [Au3(P^P^P)2](3+) (P^P^P = PPh2CH2PPhCH2PPh2). The clusters [Au4(P^P^P)2(C2R)2](2+) [R = Ph (1), biphenyl (2), terphenyl (3), C6H4OMe (4), C6H4NMe2 (5), C6H11O (6), and C6H4CF3 (7)] and [Au4(P^P^P)2(SPh)2](2+) (8) were characterized by X-ray crystallography in the solid state. NMR spectroscopic investigations in solution revealed that the majority of alkynyl clusters 1-7 exist as two isomeric species in slow chemical equilibria. All complexes 1-8 exhibit moderate-to-strong photoemission in the solid state with quantum yields from 0.07 to 0.51. The luminescence behavior was rationalized using quantum chemical density functional theory methods. The high emission efficiency of these tetragold(I) compounds and their good stability in film allowed for the fabrication of an organic electroluminescent device (OLED). Employing complex 5 (Φ = 0.51), an OLED was fabricated under a solution process to give a good external quantum efficiency of 3.1%, corresponding to a current efficiency of 6.1 cd/A and a power efficiency of 5.3 lm/W, with Commission Internationale de I'Eclairage coordinates of (0.52, 0.46).

Exciplex-forming cohost systems with 2,7-dicyanofluorene acceptors for high efficiency red and deep-red OLEDs.

Two 2,7-dicyaonfluorene-based molecules 27-DCN and 27-tDCN are utilized as acceptors (A) to combine with hexaphenylbenzene-centered donors (D) TATT and DDT-HPB for probing the exciplex formation. The photophysical characteristics reveal that the steric hindered 27-tDCN not only can increase the distance of D and A, resulting in a hypsochromic emission, but also dilute the concentration of triplet excitons to suppress non-radiative process. The 27-tDCN-based exciplex-forming blends exhibit better photoluminescence quantum yield (PLQY) as compared to those of 27-DCN-based pairs. In consequence, among these D:A blends, the device employing DDT-HPB:27-tDCN blend as the emissiom layer (EML) exhibits the best EQE of 3.0% with electroluminescence (EL) λmax of 542 nm. To further utilize the exciton electrically generated in exciplex-forming system, two D-A-D-configurated fluorescence emitter DTPNT and DTPNBT are doped into the DDT-HPB:27-tDCN blend. The nice spectral overlap ensures fast and efficient Förster energy transfer (FRET) process between the exciplex-forming host and the fluorescent quests. The red device adopting DDT-HPB:27-tDCN:10 wt% DTPNT as the EML gives EL λmax of 660 nm and maximum external quantum efficiency (EQEmax) of 5.8%, while EL λmax of 685 nm and EQE of 5.0% for the EML of DDT-HPB:27-tDCN:10 wt% DTPNBT. This work manifests a potential strategy to achieve high efficiency red and deep red OLED devices by incorporating the highly fluorescent emitters to extract the excitons generated by the exciplex-forming blend with bulky acceptor for suppressing non-radiative process.

Entropy-driven charge-transfer complexation yields thermally activated delayed fluorescence and highly efficient OLEDs.

Exciplex-forming systems that display thermally activated delayed fluorescence are widely used for fabricating organic light-emitting diodes. However, their further development can be hindered through a lack of structural and thermodynamic characterization. Here we report the generation of inclusion complexes between a cage-like, macrocyclic, electron-accepting host (A) and various N-methyl-indolocarbazole-based electron-donating guests (D), which exhibit exciplex-like thermally activated delayed fluorescence via a through-space electron-transfer process. The D/A cocrystals are fully resolved by X-ray analyses, and UV-visible titration data show their formation to be an endothermic and entropy-driven process. Moreover, their emission can be fine-tuned through the molecular orbitals of the donor. Organic light-emitting diodes were fabricated using one of the D/A systems, and the maximum external quantum efficiency measured was 15.2%. An external quantum efficiency of 10.3% was maintained under a luminance of 1,000 cd m-2. The results show the potential of adopting inclusion complexation to better understand the relationships between the structure, formation thermodynamics and properties of exciplexes.

High-performance near-infrared OLEDs maximized at 925 nm and 1022 nm through interfacial energy transfer.

Using a transfer printing technique, we imprint a layer of a designated near-infrared fluorescent dye BTP-eC9 onto a thin layer of Pt(II) complex, both of which are capable of self-assembly. Before integration, the Pt(II) complex layer gives intense deep-red phosphorescence maximized at ~740 nm, while the BTP-eC9 layer shows fluorescence at > 900 nm. Organic light emitting diodes fabricated under the imprinted bilayer architecture harvest most of Pt(II) complex phosphorescence, which undergoes triplet-to-singlet energy transfer to the BTP-eC9 dye, resulting in high-intensity hyperfluorescence at > 900 nm. As a result, devices achieve 925 nm emission with external quantum efficiencies of 2.24% (1.94 ± 0.18%) and maximum radiance of 39.97 W sr-1 m-2. Comprehensive morphology, spectroscopy and device analyses support the mechanism of interfacial energy transfer, which also is proved successful for BTPV-eC9 dye (1022 nm), making bright and far-reaching the prospective of hyperfluorescent OLEDs in the near-infrared region.

Mitochondrial dysfunction promotes cell migration via reactive oxygen species-enhanced ß5-integrin expression in human gastric cancer SC-M1 cells.

BACKGROUND: Mitochondrial dysfunction has been shown to promote cancer cell migration. However, molecular mechanism by which mitochondrial dysfunction enhances gastric cancer (GC) cell migration remains unclear. METHODS: Mitochondria specific inhibitors, oligomycin and antimycin A, were used to induce mitochondrial dysfunction and to enhance cell migration of human gastric cancer SC-M1 cells. Antioxidant N-acetylcysteine (NAC) was used for evaluating the effect of reactive oxygen species (ROS). Protein expressions of epithelial-to-mesenchymal transition (EMT) markers and the cell-extracellular matrix (ECM) adhesion molecules, the integrin family, were analyzed. A migratory subpopulation of SC-M1 cells (SC-M1-3rd) was selected using a transwell assay for examining the association of mitochondrial bioenergetic function, intracellular ROS content and ß5-integrin expression. Clinicopathologic characteristics of ß5-integrin expression were analyzed in GC specimens by immunohistochemical staining. RESULTS: Treatments with mitochondrial inhibitors elevated mitochondria-generated ROS and cell migration of SC-M1 cells. The protein expression of ß5-integrin and cell surface expression of αvß5-integrin were upregulated, and which were suppressed by NAC. Pretreatments with NAC and anti-αvß5-integrin neutralizing antibody respectively prevented the mitochondrial dysfunction-induced cell migration. The selected migratory SC-M1-3rd cells showed impaired mitochondrial function, higher mitochondria-generated ROS, and increased ß5-integrin expression. The migration ability was also repressed by anti-αvß5-integrin neutralizing antibody. In clinical specimens, GCs with higher ß5-integrin protein expression had more aggressive behavior. In conclusion, mitochondrial dysfunction may lead to GC progression by enhancing migration through mitochondria-generated ROS mediated ß5-integrin expression. GENERAL SIGNIFICANCE: These results support the role of mitochondrial dysfunction in GC progression.

Molecular topology tuning of bipolar host materials composed of fluorene-bridged benzimidazole and carbazole for highly efficient electrophosphorescence.

Two new molecules, CzFCBI and CzFNBI, have been tailor-made to serve as bipolar host materials to realize high-efficiency electrophosphorescent devices. The molecular design is configured with carbazole as the hole-transporting block and N-phenylbenzimidazole as the electron-transporting block hybridized through the saturated bridge center (C9) and meta-conjugation site (C3) of fluorene, respectively. With structural topology tuning of the connecting manner between N-phenylbenzimidazole and the fluorene core, the resulting physical properties can be subtly modulated. Bipolar host CzFCBI with a C connectivity between phenylbenzimidazole and the fluorene bridge exhibited extended π conjugation; therefore, a low triplet energy of 2.52 eV was observed, which is insufficient to confine blue phosphorescence. However, the monochromatic devices indicate that the matched energy-level alignment allows CzFCBI to outperform its N-connected counterpart CzFNBI while employing other long-wavelength-emitting phosphorescent guests. In contrast, the high triplet energy (2.72 eV) of CzFNBI imparted by the N connectivity ensures its utilization as a universal bipolar host for blue-to-red phosphors. With a common device configuration, CzFNBI has been utilized to achieve highly efficient and low-roll-off devices with external quantum efficiency as high as 14 % blue, 17.8 % green, 16.6 % yellowish-green, 19.5 % yellow, and 18.6 % red. In addition, by combining yellowish-green with a sky-blue emitter and a red emitter, a CzFNBI-hosted single-emitting-layer all-phosphor three-color-based white electrophosphorescent device was successfully achieved with high efficiencies (18.4 %, 36.3 cd A(-1) , 28.3 lm W(-1) ) and highly stable chromaticity (CIE x=0.43-0.46 and CIE y=0.43) at an applied voltage of 8 to 12 V, and a high color-rendering index of 91.6.

Modifications of Pyridine-3,5-dicarbonitrile Acceptor for Highly Efficient Green-to-Red Organic Light-Emitting Diodes.

The strategy of acceptor modification is a powerful technique for tuning the emission color of thermally activated delayed fluorescence (TADF) emitters. In this study, we have successfully designed and synthesized three TADF emitters with donor-acceptor (D-A) structures using a 4-(diphenylamino)-2,6-dimethylphenyl (TPAm) donor and various pyridine-3,5-dicarbonitrile (PC) acceptor units. As a result, three compounds named TPAmbPPC, TPAm2NPC, and TPAmCPPC exhibited greenish-yellow to orange-red emissions with high photoluminescent quantum yields (76-100%) in thin films. Remarkably, a greenish-yellow device based on TPAmbPPC and TPAm2NPC showed a high maximum external quantum efficiency (EQEmax) of 39.1 and 39.0%, respectively. Furthermore, benefiting from the suitable steric hindrance between the acceptor and donor, the nondoped organic light-emitting diodes (OLEDs) based on TPAmbPPC demonstrated an exceptional EQEmax of 21.6%, indicating its promising potential as an efficient emitter for the application of OLED applications. Furthermore, orange-red OLED devices based on TPAmCPPC exhibited a high EQEmax of 26.2%, a CE of 50.1 cd A-1, and a PE of 52.4 lm W-1.

Engineering of Cyano Functionalized Benzo[d]imidazol-2-ylidene Ir(III) Phosphors for Blue Organic Light-Emitting Diodes.

In this study, we designed and synthesized three series of blue emitting homoleptic iridium(III) phosphors bearing 4-cyano-3-methyl-1-phenyl-6-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (mfcp), 5-cyano-1-methyl-3-phenyl-6-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (ofcp), and 1-(3-(tert-butyl)phenyl)-6-cyano-3-methyl-4-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (5-mfcp) cyclometalates, respectively. These iridium complexes exhibit intense phosphorescence in the high energy region of 435-513 nm in the solution state at RT, to which the relatively large T1 → S0 transition dipole moment is beneficial for serving as a pure emitter and an energy donor to the multiresonance thermally activated delayed fluorescence (MR-TADF) terminal emitters via Förster resonance energy transfer (FRET). The resulting OLEDs achieved true blue, narrow bandwidth EL with a max EQE of 16-19% and great suppression of efficiency roll-off with ν-DABNA and t-DABNA. We obtained the FRET efficiency up to 85% using titled Ir(III) phosphors f-Ir(mfcp)3 and f-Ir(5-mfcp)3 to achieve true blue narrow bandwidth emission. Importantly, we also provide analysis on the kinetic parameters involved in the energy transfer processes and, accordingly, propose feasible ways to improve the efficiency roll-off caused by the shortened radiative lifetime of hyperphosphorescence.