A deep-red fluorophore based on naphthothiadiazole as emitter with hybridized local and charge transfer and ambipolar transporting properties for electroluminescent devices.

Herein, we report the synthesis and characterization of an efficient ambipolar charge-carrier-transporting deep-red fluorophore (TPECNz) based on a donor-acceptor-donor (D-A-D)-type molecule and its application as a non-doped emitter in an organic light-emitting diode (OLED). The fluorophore TPECNz contains naphtho[2,3-c][1,2,5]thiadiazole (Nz) as a strong acceptor unit symmetrically functionalized with N-(4-(1,2,2-triphenylvinyl)phenyl)carbazole as a donor and aggregation-induced emission (AIE) luminogen. The experimental (solvatochromic and emission in THF/water mixtures studies) and theoretical investigations prove that TPECNz retains cooperative hybridized local and charge transfer (HLCT) and weak AIE features. Thanks to its D-A-D-type structure with a proper twist angle between the D and A units, a strong electron deficiency of the Nz unit, and electron-donating and hole-transporting natures of carbazole, TPECNz exhibits a strong deep red emission (λem = 648 nm) with a high fluorescence quantum yield of 96%, outstanding thermal property (Tg = 236 °C), and ambipolar charge-carrier-transporting property with a decent balance of mobility of electrons (1.50 × 10-5 cm2 V-1 s-1) and holes (4.42 × 10-6 cm2 V-1 s-1). TPECNz is successfully employed as a non-doped emitter in an OLED which displays deep red electroluminescent emission peaked at 659 nm with CIE coordinates of (0.664, 0.335)), an EQEmax of 3.32% and exciton utilization efficiency (EUE) of 47%.

Deep-Blue Triplet-Triplet Annihilation Organic Light-Emitting Diode (CIEy ≈ 0.05) Using Tetraphenylimidazole and Benzonitrile Functionalized Anthracene/Chrysene Emitters.

Herein, new deep-blue triplet-triplet annihilation (TTA) molecules, namely 4-(10-(4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenyl)anthracen-9-yl)benzonitrile (TPIAnCN) and 4-(12-(4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenyl)chrysen-6-yl)benzonitrile (TPIChCN), are designed, synthesized, and investigated as emitters for organic light-emitting diodes (OLED). TPIAnCN and TPIChCN are composed of polyaromatic hydrocarbons of anthracene (An) and chrysene (Ch) as the cores functionalized with tetraphenylimidazole (TPI) and benzonitrile (CN) moieties, respectively. The experimental and theoretical results verify their excellent thermal properties, photophysical properties, as well as electrochemical properties. Particularly, their emissions are in the deep blue region, with TTA emissions being observed in their thin films. By utilization of these molecules as emitters, deep blue TTA OLEDs with CIE coordinates of (0.15, 0.05), high external quantum efficiency of 6.84%, and high exciton utilization efficiency (ηs) of 48% were fabricated. This result manifests the potential use of chrysene as an alternate building block to formulate new TTA molecules for accomplishing high-performance TTA OLEDs.

Intrinsic Hole Mobility in Luminescent Metal-Organic Frameworks and Its Application in Organic Light-Emitting Diodes.

Most metal-organic frameworks (MOFs) lack charge mobility, which is crucial for realizing their use in optoelectronic applications. This work proposes the design of a MOF using triarylamine-based ligands (Zr-NBP) as the lone pair electron spacer to enhance the hole mobility in the MOF while maintaining its luminescent properties. Zr-NBP has strong fluorescence with a good hole mobility of 1.05×10-6  cm2 V-1 s-1 , which is comparable to organic materials used in optoelectronic devices. We also employed a Zr-NBP nanofilm in the pure phase as both a non-doped emissive layer and a hole-transporting layer within organic light-emitting diodes (OLEDs). The obtained OLED device produced a bright green light with a low turn-on voltage of 3.9 V. This work presents an advance in developing the electronic properties of MOFs by modifying the chemical properties of its building blocks, and will likely inspire further design of MOF materials as active layers in optoelectronic devices.

Highly Active Homoleptic Zinc and Magnesium Complexes Supported by Constrained Reduced Schiff Base Ligands for the Ring-Opening Polymerization of Lactide.

New homoleptic zinc and magnesium complexes containing constrained reduced Schiff base ligands based on substituted 7-hydroxy-1-indanone were successfully synthesized and used as a catalyst for the polymerization of lactide. The ligands contain a side arm having different basicity because dimethylamino, pyridyl, and furfuryl groups are shown to greatly affect the polymerization rates. The homoleptic zinc complex containing constrained reduced Schiff base ligands and a dimethylamino side arm was highly active, giving a 92% conversion of l-lactide in 3 min using [LA]:[Zn]:[BnOH] = 500:1:2 at room temperature. The polymerization is pseudo-first-order dependent on the LA concentration. Well-controlled and living behavior of the zinc complex was observed and demonstrated in the preparation of stereodiblock and triblock copolymers of l-, d-, and rac-lactide in a one-pot sequential synthesis with a predictable block length, block sequence, and narrow dispersity rapidly in 10 min. Stereocomplex formation was observed for PLA made sequentially from 100 l-LA, 100 rac-LA, and 100 d-LA having a high Tm of up to 220 °C.

Hydroxy-Tetraphenylimidazole Derivatives as Efficient Blue Emissive Materials for Electroluminescent Devices.

Herein, three hydroxy-tetraphenylimidazole (HPI)-based fluorophores (HPI-TPA, HPI-PCz, and HPI-CzP) are designed and synthesized by disubstituted HPI core with arylamine units of triphenylamine (TPA), phenyl carbazole (PCz), and carbazole phenyl (CzP) at 3,5-positions of the N-phenyl ring of HPI, respectively. Their photophysical properties are theoretically and experimentally examined. HPI-TPA shows a hybridized local and charge transfer (HLCT) excited state characteristic and emits deep blue color via an HLCT mechanism, while both HPI-PCz and HPI-CzP exhibit excited-state intramolecular proton transfer (ESIPT) property and display pure keto form emissions. They possess high thermal stability and are successfully fabricated as emitters in organic light-emitting diodes (OLEDs). All devices exhibit intense blue color emissions with low turn-on voltages (3.5-3.7 V). Particularly, HPI-TPA-based OLED emits light in the deep-blue region with a high maximum external quantum efficiency (EQEmax ) of 3.77% and a decent efficiency roll-off.

Twisted Phenanthro[9,10-d]imidazole Derivatives as Non-doped Emitters for Efficient Electroluminescent Devices with Ultra-Deep Blue Emission and High Exciton Utilization Efficiency.

Herein, two deep-blue emissive molecules (SAF-PI and SAF-DPI) are designed and synthesized using spiro[acridine-9,9'-fluorene] as a donor (D) substituted with 2-(3-methylphenyl)-1-phenyl-phenanthro[9,10-d]imidazole as an acceptor (A), forming twisted D-A and A-D-A structures, respectively. The photophysical studies and density functional theory (DFT) calculations reveal that both molecules exhibit hybridized local excited and charge transfer (HLCT) characteristics with deep blue emission color. They are effectively applied as non-doped emitters in OLEDs. Particularly, SAF-PI-based device achieves the high-definition television (HDTV) standard blue color emission peaked at 428 nm with CIE coordinate of (0.156, 0.053), a narrow full width at half maximum of 55 nm, a maximum external quantum efficiency (EQEmax ) of 4.57% and an exciton utilization efficiency of 65%.

Rational Design of Chrysene-Based Hybridized Local and Charge-Transfer Molecules as Efficient Non-Doped Deep-Blue Emitters for Simple-Structured Electroluminescent Devices.

Herein, we present a molecular design of chrysene-based deep-blue emissive materials (TC, TpPC, TpXC, and TmPC), in which chrysene as a core is functionalized with different triphenylamine moieties to realize a fine-tuning deep-blue fluorescence with superior electroluminescent (EL) performance. The photophysical analyses and density functional theory (DFT) calculations disclose that TC, TpPC, and TpXC possess HLCT characteristics with intense deep-blue emission in the solid-state, good hole-transporting ability, and high thermal and electrochemical stabilities. They are successfully employed as non-doped emitters in simple structured OLEDs (ITO/PEDOT : PSS : NF/emitter/TPBi/LiF : Al). In particular, TC-based device emits a deep-blue light with an emission peak at 446 nm and CIE color coordinates of (0.148, 0.096), a maximum external quantum efficiency (EQEmax ) of 4.31%, and a low turn-on voltage of 2.8 V.

Red to orange thermally activated delayed fluorescence polymers based on 2-(4-(diphenylamino)-phenyl)-9H-thioxanthen-9-one-10,10-dioxide for efficient solution-processed OLEDs.

Most highly efficient thermally activated delayed fluorescence (TADF)-based organic light-emitting diodes (OLEDs) are multi-layer devices fabricated by thermal vacuum evaporation techniques, which are unfavorable for real applications. However, there are only a few reported examples of efficient solution-processed TADF OLEDs, in particular TADF polymer OLEDs. Herein, a series of solution-processable TADF conjugated polymers (PCTXO/PCTXO-Fx (x = 25, 50 and 75)) were designed and synthesized by copolymerization of 2-(4-(diphenylamino)-phenyl)-9H-thioxanthen-9-one-10,10-dioxide (TXO-TPA) as a red/orange emissive TADF unit, 9,9'-((fluorene-9,9-diyl)-bis(octane-8,1-diyl))-bis(3,6-di-tert-butylcarbazole) as host/hole-transporting unit and 2,7-N-(heptadecan-9-yl)carbazole as a conjugated linker and solubilizing group. They possessed a conjugated backbone with donor TPA-carbazole/fluorene moieties and a pendent acceptor 9H-thioxanthen-9-one-10,10-dioxide (TXO) forming a twisted donor-acceptor structure. These polymers in neat films displayed red/orange color emissions (601-655 nm) with TADF properties, proved by theory calculations and transient PL decay measurements. Their hole-transporting capability was improved when the content of 9,9'-((fluorene-9,9-diyl)-bis(octane-8,1-diyl))-bis(3,6-di-tert-butylcarbazole) within the polymers increased. All polymers were successfully employed as emitters in solution-processed OLEDs. In particular, the doped OLED fabricated with PCTXO exhibited an intense deep orange emission at 603 nm with the best electroluminescence performance (a maximum external quantum efficiency 10.44%, a maximum current efficiency of 14.97 cd A-1 and a turn-on voltage of 4.2 V).

The improvement in hole-transporting and electroluminescent properties of diketopyrrolopyrrole pigment by grafting with carbazole dendrons.

Diketopyrrolopyrrole (DPP) pigments are essential and have been intensively exploited as building-blocks for the synthesis of organic semiconducting polymers and small molecules; however, DPP derivatives as emissive materials for electroluminescent (EL) devices have rarely been explored. In this work, a series of new DPP derivatives grafted with carbazole dendrons in a non-conjugated fashion using an amide linkage was designed to improve the performance of DPP in EL devices. Three DPP derivatives (G0DPP, G1DPP and G2DPP) bearing di(p-chlorophenyl)-DPP (Pigment Red 254) as the core substituted with a hexyl chain, N-hexyl carbazole and N-hexyl-N'-9,3':6',N''-tercarbazole, respectively, were synthesized to afford improved hole-transporting properties without affecting the photophysical and electronic properties of the DPP core. The synthesized DPP derivatives displayed an intense yellow fluorescence emission peaked at 536 nm with an absolute photoluminescence quantum yield close to unity in solution. The hole-transporting capability of molecules was improved when carbazole dendrons were incorporated, which increased with an increase in the generation of substituent carbazole dendrons in the order of G0DPP < G1DPP < G2DPP. Significantly, the use of G2DPP, showing the highest hole mobility, in an EL device yielded a strong and stable yellow emission peaked at 556 nm (CIE x, y color coordinates of (0.45, 0.53)) with a brightness of 3060 cd m-2, maximum luminous efficiency of 9.24 cd A-1 and a maximum EQE of 3.11%.

A highly efficient near infrared organic solid fluorophore based on naphthothiadiazole derivatives with aggregation-induced emission enhancement for a non-doped electroluminescent device.

Two regioisomers of naphthothiadiazole derivatives with aggregation-induced emission enhancement exhibited a strong solid-state fluorescence emission in the range of 666-760 nm. A non-doped EL device emitted brilliant near infrared emission peaked at 754 nm with a high maximum radiance of 22 050 mW Sr-1 m-2, an EQE as high as 1.48%, and relatively low efficiency roll-off.

A Simple and Strong Electron-Deficient 5,6-Dicyano[2,1,3]benzothiadiazole-Cored Donor-Acceptor-Donor Compound for Efficient Near Infrared Thermally Activated Delayed Fluorescence.

Despite the success of thermally activated delayed fluorescent (TADF) materials in steering the next generation of organic light-emitting diodes (OLEDs), effective near infrared (NIR) TADF emitters are still very rare. Here, we present a simple and extremely high electron-deficient compound, 5,6-dicyano[2,1,3]benzothiadiazole (CNBz), as a strong electron-accepting unit to develop a sufficiently strong donor-acceptor (D-A) interaction for NIR emission. End-capping with the electron-donating triphenylamine (TPA) unit created an effective D-A-D type system, giving rise to an efficient NIR TADF emissive molecule (λem =750 nm) with a very small ΔEST of 0.06 eV. The electroluminescent device using this NIR TADF emitter exhibited an excellent performance with a high maximum radiance of 10020 mW Sr-1 m-2 , a maximum EQE of 6.57% and a peak wavelength of 712 nm.

QM/MM molecular modelling on mutation effect of chorismate synthase enzyme catalysis.

Chorismate synthase (CS) catalyzes the conversion of 5-enolpyruvylshikimate-3-phosphate (EPSP) to chorismate which is a key intermediate in the biosynthesis of aromatic amino acids. CS enzyme is a new target for antibacterial drugs. Even though several reaction mechanisms have been proposed, the catalytic mechanism is still unclear. QM/MM adiabatic mapping calculations were performed in order to investigate roles of this enzyme. High-accuracy SCS-MP2/aVDZ/CHARMM27 calculations indicated that the reaction pathway has three steps; (i) proton transfer from reduced flavin mononucleotide (FMNH2) to D339, (ii) proton transfer from EPSP to FMNH- and (iii) phosphate elimination. Adiabatic mapping calculations indicated that H110 and R48 residues play essential catalyst roles for CS enzyme catalysis by transition state (TS) and product stabilizations via charge polarization and hydrogen bonding to EPSP and/or FMNH2. A high accuracy calculation - SCS-MP2/aVDZ/CHARMM27 method was employed to obtain the accurate reaction mechanism pathway and to evaluate the effect of amino acid residues in the active site on the enzyme catalysis. The potential energy barriers of the reactions of H110A and R48A were found to increase. The CS catalysis was consequently slowed down due to missing the TS and product stabilizations.