Synthesis of 5-(Aryl)amino-1,2,3-triazole-containing 2,1,3-Benzothiadiazoles via Azide-Nitrile Cycloaddition Followed by Buchwald-Hartwig Reaction.

An efficient access to the novel 5-(aryl)amino-1,2,3-triazole-containing 2,1,3-benzothiadiazole derivatives has been developed. The method is based on 1,3-dipolar azide-nitrile cycloaddition followed by Buchwald-Hartwig cross-coupling to afford the corresponding N-aryl and N,N-diaryl substituted 5-amino-1,2,3-triazolyl 2,1,3-benzothiadiazoles under NHC-Pd catalysis. The one-pot diarylative Pd-catalyzed heterocyclization opens the straightforward route to triazole-linked carbazole-benzothiadiazole D-A systems. The optical and electrochemical properties of the compound obtained were investigated to estimate their potential application as emissive layers in OLED devises. The quantum yield of photoluminescence (PLQY) of the synthesized D-A derivatives depends to a large extent on electron-donating strengths of donor (D) component, reaching in some cases the values closed to 100%. Based on the most photoactive derivative and wide bandgap host material mCP, a light-emitting layer of OLED was made. The device showed a maximum brightness of 8000 cd/m2 at an applied voltage of 18 V. The maximum current efficiency of the device reaches a value of 3.29 cd/A.

Charge Carrier Mobility in Poly(N,N'-bis-4-butylphenyl-N,N'-bisphenyl)benzidine Composites with Electron Acceptor Molecules.

Polymer composites based on poly(N,N'-bis-4-butylphenyl-N,N'-bisphenyl)benzidine (poly-TPD) with PCBM and copper(II) pyropheophorbide derivative (Cu-PP) were developed. In thin films of the poly-TPD and Cu-PP composites, the charge carrier mobility was investigated for the first time. In the ternary poly-TPD:PCBM:Cu-PP composite, the electron and hole mobilities are the most balanced compared to binary composites and the photoconductivity is enhanced due to the sensitization by Cu-PP in blue and red spectral ranges. The new composites are promising for use in the development of photodetectors.

Synthesis, Photo- and Electroluminescence of New Polyfluorene Copolymers Containing Dicyanostilbene and 9,10-Dicyanophenanthrene in the Main Chain.

Using palladium-catalyzed Suzuki polycondensation, we synthesized new light-emitting fluorene copolymers containing the dicyano derivatives of stilbene and phenanthrene and characterized them by gel permeation chromatography, UV-vis absorption spectroscopy, spectrofluorimetry, and cyclic voltammetry. The photoluminescence spectra of the synthesized polymers show significant energy transfer from the fluorene segments to the dicyanostilbene and 9,10-dicyanophenanthrene units, which is in agreement with the data of theoretical calculations. OLEDs based on these polymers were fabricated with an ITO/PEDOT-PSS (35 nm)/p-TPD (30 nm)/PVK (5 nm)/light emitting layer (70-75 nm)/PF-PO (20 nm)/LiF (1 nm)/Al (80 nm) configuration. Examination of their electroluminescence revealed that copolymers of fluorene with dicyanostilbene show yellow-green luminescence, while polymers with 9,10-dicyanophenanthrene have a greenish-blue emission. The 9,10-dicyanophenanthrene units have a more rigid structure compared to dicyanostilbene and, in OLEDs based on them, an increase in maximum brightness is observed with an increase in the content of the additive to the polymer chain. In particular, the device using fluorene copolymer with 9,10-dicyanophenanthrene (2.5 mol%) exhibited a maximum brightness of 9230 cd/m2 and a maximum current efficiency of 3.33 cd/A.

New Unsymmetrically Substituted Benzothiadiazole-Based Luminophores: Synthesis, Optical, Electrochemical Studies, Charge Transport, and Electroluminescent Characteristics.

Three new benzothiadiazole (BTD)-containing luminophores with different configurations of aryl linkers have been prepared via Pd-catalyzed cross-coupling Suzuki and Buchwald-Hartwig reactions. Photophysical and electroluminescent properties of the compounds were investigated to estimate their potential for optoelectronic applications. All synthesized structures have sufficiently high quantum yields in film. The BTD with aryl bridged carbazole unit demonstrated the highest electrons and holes mobility in a series. OLED with light-emitting layer (EML) based on this compound exhibited the highest brightness, as well as current and luminous efficiency. The synthesized compounds are not only luminophores with a high photoluminescence quantum yield, but also active transport centers for charge carriers in EML of OLED devices.

Effect of Cp-Ligand Methylation on Rhodium(III)-Catalyzed Annulations of Aromatic Carboxylic Acids with Alkynes: Synthesis of Isocoumarins and PAHs for Organic Light-Emitting Devices.

An efficient protocol was developed for the synthesis of π-extended isocoumarins and polycyclic aromatic hydrocarbons based on the oxidative coupling of aromatic carboxylic acids with internal alkynes catalyzed by (cyclopentadienyl)rhodium complexes. The coupling chemoselectivity strongly depends on whether Cp or the methylated Cp* ligands are used. The pentamethyl derivative [Cp*RhCl2 ]2 predominantly gives isocoumarins, while the non-methylated complex [CpRhI2 ]n produces naphthalene derivatives. The polyaromatic carboxylic acids (such as 1-naphthoic acid, 1-pyrenecarboxylic acid, fluorene-1-carboxylic acid, and dibenzofuran-4-carboxylic acid) are suitable for this approach. A mixture of Cp*H/RhCl3 can be used as a catalyst instead of [Cp*RhCl2 ]2 . The structures of 3,4-diphenylindeno[1,2-h]isochromen-1(11H)-one and 7,10-dimethyl-8,9-diphenylbenzo[pqr]tetraphene were determined by X-ray diffraction. In addition, the optical properties of the prepared compounds were studied. 7,8-Diphenyl-10H-phenaleno[1,9-gh]isochromen-10-one was employed as an emissive layer for OLED manufacturing. The OLED emits yellow-green light with a maximum intensity 1740 cd ⋅ m-2 at 15 V.

LMCT facilitated room temperature phosphorescence and energy transfer in substituted thiophenolates of Gd and Yb.

To obtain luminescent lanthanide complexes with a low energy LMCT state the 2-(2'-mercaptophenyl)benzothiazolates, Ln(SSN)3, and 2-(2'-mercaptophenyl)benzoxazolates, Ln2(OSN)6 (Ln = Gd, Yb), were synthesized by the reaction of amides Ln[N(SiMe3)2]3 with respective thiophenols. Ytterbium complexes were structurally characterized by X-ray diffraction analysis. Cyclic voltammetry revealed that the deprotonated mercaptophenyl ligands have significantly lower oxidation potentials than their phenoxy analogues and some ß-diketones. The photophysical properties of Gd and Yb compounds were studied both in solution and in the solid state. The fluorescence spectra of the compounds in solution display the bands of the keto and enol forms of the ligands. No energy transfer from the organic part to Yb3+ has been detected in solutions of both Yb complexes, whereas in solids an intense metal-centered emission in the near infrared region was observed. The solid Gd compounds exhibited room temperature phosphorescence caused by unusually efficient intersystem crossing facilitated by the essentially reducing properties of OSN and SSN ligands. To explain the sensitization process occurring in solids Yb2(OSN)6 and Yb(SSN)3 a specific non-resonant energy transfer mechanism via a ligand to metal charge transfer state has been proposed. Based on the Yb derivatives, NIR-emitting OLEDs with 860 µW cm-2 maximal irradiance were obtained. Their Gd counterparts showed bright electrophosphorescence (up to 1350 cd m-2) in the devices containing doped emission layers.