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A series of new iridium(iii) cyclometalated complexes (4tfmpiq)2Ir(tiptha), (4tfmpiq)2Ir(phdiptha), (4tfmpiq)2Ir(fphdiptha) and (4tfmpiq)2Ir(ipdptha) (4tfmpiq = 4-(4-(trifluoromethyl)phenyl)isoquinoline, tiptha = 1,1,3-triisopropylthiourea, phdiptha = 1,1-diisopropyl-3-phenylthiourea, fphdiptha = 3-(4-fluorophenyl)-1,1-diisopropylthiourea, ipdptha = 3-isopropyl-1,1-diphenylthiourea) containing a unique four-membered ring Ir-S-C-N backbone were facilely synthesized under mild conditions. By introducing different substituents such as isopropyl, phenyl, 4-fluorophenyl, diisopropylamine and diphenylamine on the thiourea ancillary ligands, not only the S-C-N ligands can be extensively derived, but also the emission colors (lambdapeak = 627-636 nm) and photoluminescence quantum efficiencies (PhiP = 38.0-42.0%) can be regulated. Employing these complexes as emitters, the organic light emitting diodes (OLEDs) exhibited good performances with a maximum external quantum efficiency (EQEmax) of 13.1% for saturated red emission with CIE coordinates of (0.68, 0.32). These results demonstrate the great potential of the S-C-N ancillary ligands for developing new Ir(iii) complexes towards OLED applications.

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Reference:
Isoquinoline – Wikipedia,
Isoquinoline | C9H1376N – PubChem

 

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We describe herein an air stable phosphorus ligand for both Suzuki-Miyaura and Buchwald-Hartwig palladium-catalyzed cross coupling reactions. The versatility of the Pd(dba)2-di-tert-butyl N,N-diethylphosphoramidite catalytic system is demonstrated for a variety of aryl and heteroaryl halides. This ligand is ??bench stable?? which allows easy catalyst preparation. Moreover, even at low catalyst loadings (0.5 %), excellent yields are usually achieved.

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The invention relates to a N – hetero aryl carbazole compound of preparation method: to carbazole compound and heteroaryl halide as raw materials, Cu (I) salt as catalyst, 1 – methyl imidazole-ligand, in the presence of alkaline material uncle butanol lithium protection of nitrogen conditions for 110 – 130 C in an organic solvent in the reaction 1.2 hours -5.0 days, to be after the reaction, the reaction mixture separation and purification, formula (I), formula (II) or formula (III) shown in the carbazole compound N – heteroaryl; the hetero aryl halide is heteroaryl bromide or heteroaryl iodides. The invention cheap price of raw materials, the reaction process and the operation is simple, a yield as high as 90% or more and is suitable for large-scale preparation and industrialization, it has broad application prospects. (by machine translation)

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A substance that facilitates hole injection and has high triplet excitation energy is provided. A light-emitting element having high emission efficiency is provided. A light-emitting element driven with a low voltage is provided. Or a light-emitting element having a long lifetime is provided. Provided is a light-emitting element including a triazolo[4,3-f]phenanthridine derivative or a triazolo[3,4-a]isoquinoline derivative. Provided is a triazolo[4,3-f]phenanthridine and triazolo[3,4-a]isoquinoline derivatives, which are novel and can be used for the light-emitting element.

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A series of rigid planar azadiindoles (8a, 8b, and 8d), benzannelated pyridodiindoles (11a, 11b, and 11d), and indolopyridoimidazoles (11c, 20, and 24) were synthesized from 4-oxo-1,2,3,4-tetrahydro-beta-carboline 5 via the Fischer indole cyclization with the appropriate arylhydrazines. These analogues were employed as probes (‘molecular yardsticks’) to define the spatial dimensions of the lipophilic regions of the benzodiazepine receptor (BzR) binding cleft. Benzannelated indoles 11a-d and indolopyridoimidazoles 20 and 24 were important in establishing an area of negative interaction (S1, see Figure 6, part b) in the binding cleft common to the interactions of both inverse agonists and agonists. Data from this chemical and computer- assisted analysis of the pharmacophore (see Figure 6) indicates that inverse agonists and agonists bind to the same binding region, but the pharmacophoric descriptors required for the two activities are different, in keeping with previous studies with these planar ligands. However, the hydrogen bond donating site H1 and the lipophilic region L1 in the receptor binding site are common interactions experienced by both series of ligands. The low affinities of both indolo[3,2-c]carbazole (3a) and indolo[3,2-b]isoquinoline (3b) for the BzR are consonant with the requirements of a hydrogen bond acceptor interaction at donor site H1 and a hydrogen bond donor interaction at acceptor site A2 for potent inverse agonist activity in the beta-carboline series. The hydrochloride salts of 1-aza- 8a (IC50 10.6 nM), 2-aza- 8b (IC50 51.5 nM), and 4-azadiindole 8d (IC50 11.2 nM) were found to be much more soluble in water than the corresponding salt of the parent diindole 2. Moreover, aza analogues 8a and 8b were shown to be partial inverse agonists with proconvulsant potencies comparable to that of the parent diindole 2.

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Traditional methods for the preparation of secondary alkyl-substituted aryl and heteroaryl chlorides challenge both selectivity and functional group tolerance. This contribution describes the use of statistical design of experiments to develop an effective procedure for the preparation of isopropyl-substituted (hetero)arenes with minimal isopropyl to n-propyl isomerization. The reaction tolerates electronically diverse aryl chloride coupling partners, with excellent conversion observed for strongly electron-deficient aromatic rings, such as esters and amides. Electron-rich systems, including methyl- and methoxy-substituted aryl chlorides, were found to be less reactive. Furthermore, the reaction was found to be most successful when heteroaryl chlorides were submitted to the cross-coupling protocol. By mapping substituent effects on reaction selectivity, we were able to show that electron-deficient aryl chlorides are essential for efficient coupling, and use electronic structure calculations to predict the likelihood of successful coupling through the estimation of the electron affinity of each aryl chloride. Moderate isolated yields were achieved with selected aryl chlorides, and moderate to good isolated yields were obtained for all the heteroaryl chlorides coupled. Excellent selectivity was observed when a 2,6-dichloroquinoline was used, allowing mono-substitution on a challenging substrate. (Figure presented.).

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A new Fe- or Co-catalyzed Cl/Zn-exchange reaction allows the direct transformation of aryl, heteroaryl, and also alkyl chlorides into the corresponding zinc reagents. The method tolerates functional groups such as a nitrile or an ester. Remarkably, secondary and tertiary alkyl chlorides are suitable substrates for the Cl/Zn exchange.

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A new phosphorescent (CQ-BP)2Ir(acac), (CMQ-BP)2Ir(acac), (BQ-BP)2Ir(acac) was synthesized for organic light-emitting diodes (OLEDs). OLEDs using phosphorescent iridium(III) complexes attract enormous attention because they allow highly efficient electro phosphorescence. The donor-acceptor type ligands for the Iridium(III) complexes were synthesized by Suzuki coupling reaction. The ligands through changes in oxidative addition materials (electron-acceptor) and organic borane (electron-donor) to get the red color were to study the appropriate Iridium(III) complexes. Oxidative addition materials were used such as 2-chloro-4-methylquinoline, 1-chloroisoquinoline and 2-bromoquinoline. 4-tert-Butylphenyl-boronic acid was used as organic borane. The dopant was synthesized by Nonoyama reaction. Red dopants were observed with an emission peak at approximately 600 nm. Iridium(III) complexes were measured by nuclear magnetic resonance (NMR), UV-visible spectroscopy and photoluminescence (PL). The phosphorescence emission maxima were dependent on the electron density of donor and acceptor moiety of the ligands.

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A single set of reaction conditions for the palladium-catalyzed amination of a wide variety of (hetero)aryl halides using primary alkyl amines has been developed. By combining the exceptionally high reactivity of the Pd-PEPPSI-IPentCl catalyst (PEPPSI=pyridine enhanced precatalyst preparation, stabilization, and initiation) with the soluble and nonaggressive sodium salt of BHT (BHT=2,6-di-tert-butyl-hydroxytoluene), both six- and five-membered (hetero)aryl halides undergo efficient and selective amination.

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Four new dyes that derive from borylated arylisoquinolines were prepared, containing a third aryl residue (naphthyl, 4-methoxy-naphthyl, pyrenyl or anthryl) that is linked via an additional stereogenic axis. The triaryl cores were synthesized by Suzuki couplings and then transformed into boronic acid esters by employing an Ir(I)-catalyzed reaction. The chromophores show dual emission behavior, where the long-wavelength emission band can reach maxima close to 600 nm in polar solvents. The fluorescence quantum yields of the dyes are generally in the range of 0.2?0.4, reaching in some cases values as high as 0.5?0.6. Laser-flash photolysis provided evidence for the existence of excited triplet states. The dyes form fluoroboronate complexes with fluoride anions, leading to the observation of the quenching of the long-wavelength emission band and ratiometric response by the build-up of a hypsochromically shifted emission signal.

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