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To explore the photophysical properties of coordination compounds with bright blue fluorescence, an azomethin-zinc complex was synthesized and characterized by various techniques (elemental analysi ...

Derivatives of indole and benzo[b]carbazole were prepared by employing efficient regioselective acid-catalysed synthesis of 1H, 1-methyl and 1-naphthylindole with o-phthaldialdehyde. The synthesized compounds were characterized by NMR, IR and mass spectrometries. They form molecular glasses with glass transition temperatures ranging from 86 to 116 °C. Naphthyl-substituted derivatives showed high thermal stabilities with 5% weight loss temperatures of 409 and 413 °C, while their methyl-substituted counterparts exhibited by ca. 90 °C lower 5% weight loss temperatures. Their solutions exhibited blue emission with quantum yields of 67%. Ionization potentials of the compounds estimated by cyclic voltammetry are in the range of 5.49–5.65 eV, while the values obtained using photoelectron emission in air method are in the range of 5.16–5.28 eV. The layers of the compounds exhibited ambipolar charge transport with time-of-flight charge drift mobility values well exceeding 10−3 cm2/(Vs) at high electric fields. Non-doped naphthylindole and benzo[b]carbazole derivative based device emitted deep-blue light with the maximum intensity at 410 nm and CIE of (0.21, 0.16), and it exhibited a maximum external quantum efficiency of 3.4%.

New donor-acceptor and donor-acceptor-donor compounds based on perfluorobiphenyl electron acceptor and diphenylamine or carbazole as electron-donating units were designed, synthesized and characterized. The influence of the nature and number of electron-donating units on thermal, electrochemical and photophysical properties was studied. The compounds exhibited photoluminescence ranging from near-UV to green region. The solid samples of the compounds demonstrated photoluminescence quantum yields in the range from 0.1 to 0.51.2,7-Dimethoxycarbazole-containing compound was characterized by negligible energy gaps between the lowest singlet and triplet states (0.1 eV) and subsequently showed thermally activated delayed fluorescence (TADF). Carbazolyl-substituted perfluorobiphenyl derivatives showed aggregation-induced emission enhancement and high values of the energies of triplet levels (up to 3.08 eV). The derivatives exhibited from moderate to high temperatures of 5% weight loss up to 356 °C. Electron mobility up to 1.2 × 10−4 cm2 V−1 s−1 at electric field of 7 × 105 V/cm was detected for the studied compounds by time-of-flight measurements. One compound with the best combination of the required properties for the OLED hosts was selected for the fabrication of green TADF-based OLED. The device showed maximum external quantum efficiency of 15.1%. Another compound exhibiting efficient TADF demonstrated oxygen sensitivity with non-linear Stern-Volmer curve which was well fitted by two Stern-Volmer constants of 6.54·10−4 and 7.17·10−6 ppm−1.

Elaboration of the appropriate host materials proved to be not less important for the fabrication of a highly efficient OLED than the design of emitters. In the present work, we show how by simple variation of molecular structure both blue emitters exhibiting delayed fluorescence and ambipolar high triplet energy hosts can be obtained. The compounds with a para-junction revealed higher thermal stability (TID up to 480 °C), lower ionization potentials (5.51–5.60 eV), exclusively hole transport, and higher photoluminescence quantum efficiencies (0.90–0.97). Meta-linkage leads to ambipolar charge transport and higher triplet energies (2.82 eV). Introduction of the accepting nitrile groups in the para-position induces intensive delayed fluorescence via a triplet–triplet annihilation up-conversion mechanism. By utilization of the para-substituted derivative as an emitter and the meta-substituted isomer as the host, a deep-blue OLED with the external quantum efficiency of 14.1% was fabricated.

A new series of TADF emitters with donor-acceptor or donor-acceptor-donor structure containing 2,7-dimethoxycarbazole donor moiety and diphenylsulfone acceptor unit were synthesized and employed in non-doped sky-blue organic light emitting diodes with the external quantum efficiency reaching 9.0%. Thermal, optical and photophysical properties of for D-A and D-A-D compounds containing one or two tert-butyl groups attached to C-3 and C-6 positions of 2,7-dimethoxycarbazole moiety were studied and compared with those of the corresponding compounds containing no tert-butyl groups. Studies of photophysical properties of the compounds confirmed TADF nature of their emission. Computational studies revealed that small modification of the donor moiety could have a significant impact on the TADF mechanism turning it from vibronically induced TADF mediated by the T2 state to the common TADF which occurs through the direct reverse intersystem crossing between the S1 and T1 states. New principle of purposeful of molecular design of TADF emitters with controlled efficiency of reverse intersystem crossing by only small functionalization of donor fragments is proposed.

A new class of carbazole derivatives, with varying degree of core substitution was synthesized and characterized. The presented synthetic route requires mild conditions, starts from low-cost substrates and leads to the formation of the target products with good yields. The optical and electronic properties of the synthesized materials were estimated and supported by DFT calculations. Investigated compounds emit violet light with quantum efficiency reaching 18.2%. Electrochemical and electron photoemission spectroscopy revealed that ionization potentials are in range of 5.10–5.30 eV. Time-of-flight measurements revealed that those compounds have balanced hole and electron mobility in range of 4.27·10−6–8.42·10‐5 cm2/Vs for star-shaped compound and 6.2 × 10−7–6.2 × 10−6 cm2/Vs for linear derivatives. Electroluminescence spectra of the OLED device prepared using the newly synthesized compounds were characterized by broad emission in visible range, resulting in white light generation.

A new ambipolar fluorophore, 3,6-di(4,4′-dimethoxydiphenylaminyl)-9-(1-naphthyl)carbazole, was synthesized and its physical properties were studied by differential scanning calorimetry, thermogravimetric analysis, UV-vis absorption, luminescence and photoelectron emission spectroscopy, cyclic voltammetry and a time of flight method. The latter technique indicates that the compound demonstrates bipolar semiconducting properties. Using the synthesized compound as an emissive material, a single-layer OLED with an electroluminescence spectrum containing a voltage-dependent electroplex emission band in the region of 550–650 nm was fabricated. Another OLED was fabricated with an additional electron transporting bathophenanthroline layer that forms a direct interface with the layer of 3,6-di(4,4′-dimethoxydiphenylaminyl)-9-(1-naphthyl)carbazole. A strong exciplex-type band in the electroluminescence spectrum of this OLED with an emission maximum at ca. 540 nm was observed. The electroluminescence spectra of both devices were found to be clearly dependent on the applied bias. This effect can be useful for the development of efficient and colour-tunable OLEDs.

Materials with high triplet energies have attracted great attention for their application in exciplex-based or thermally activated delayed fluorescence-based organic light-emitting diodes. To study the correlation between triplet energy and chemical structure, six compounds with typical donor-acceptor-donor structures were designed, synthesized, and characterized. Through the adjustment of molecular configuration by weakening the strengths of donors and increasing the angles between donors and acceptors, the triplet energies of the materials were gradually increased from 2.5 to 3.0 eV. Three exciplex-based organic light-emitting diodes containing one of the synthesized compounds were fabricated, which exhibited efficient blue, green-yellow, and white thermally activated delayed fluorescence. Blue and green-yellow organic light-emitting diodes exhibited the maximum external quantum efficiencies of 9.1% and 8.3%, respectively. White organic light-emitting diodes showed turn-on voltage of 4.8 V, high maximum luminance of 18474 cdm-2, and maximum external quantum efficiency of 10.6%. Maximum external quantum efficiencies of blue and white organic light-emitting diodes were close to the record values observed for all-exciplex-based blue and white organic light-emitting diodes.

CdTe/CdS core-shell quantum dots were synthesized and implemented into a light emitting device resulting in multi-channel electroluminescence with a light-green emission colour. The main electroluminescence band at about 530 nm corresponds to the emission by the CdTe core (type I core/shell structure), while the next emission band at 595 nm is assigned to the crossed recombination of electrons from the conduction band of the CdS shell and holes from the valence band of the CdTe core (type II core/shell structure). At the same time, the photoluminescence spectrum of the synthesized CdTe/CdS core-shell quantum dots contains only one emission band distinctive for type II structures. This behavior of CdTe/CdS core-shell quantum dots upon the electroexcitation allows the extension of the electroluminescence spectrum in the optical region in a way that is useful for the lighting-source applications. Such multi-channel electroluminescence can most probably also be reproduced in related core-shell systems accounting for size-confinement between the core size and shell thickness.

A new triaryl molecule based on a benzene–benzothiadiazole–benzene core has been applied in a WOLED device. This very simple molecule emits from a combination of emissive states (exciton/electromer/exciplex/electroplex) to give white light with CIE coordinates of (0.38, 0.45) and a colour temperature of 4500 K.

Series of compounds consisting of carbazole arms and 1,3,5-triazine core linked by amino group were synthesized and characterized. The clear relationship between electrochemical properties, quantum efficiency, charge transport properties and structure were estimated. The exciplex-forming properties of the synthesized compound as donor, and two known exciplex-forming acceptors 4,7-diphenyl-1,10-phenanthroline (Bphen) and 2,2′,2"-(1,3,5-benzenetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi) where predicted and investigated. It was shown that the star-shaped configuration of the compound 3CzNCprovides the best exciplex OLED performance with EQE up to 6.84%.

The bicarbazole derivative 4,4'-(9H, 9'H-[3,3'-bicarbazole]-9,9'-diyl) bis(3-(trifluoromethyl) benzonitrile), denoted as pCNBCzoCF(3), was synthesized and tested for white OLED applications. pCNBCzoCF3 demonstrated an extremely small value of the singlet-triplet energy gap that caused intensive thermally activated delayed fluorescence (TADF). In addition, this compound is able to form exciplex-type excited states at the interface with star-shaped 4,40,400-tris[phenyl(m-tolyl) amino] triphenylamine (m-MTDATA). Combining the TADF emission of pCNBCzoCF3 with the exciplex emission from the pCNBCzoCF(3) m-MTDATA interface, we fabricated a number of highly efficient "warm-white'' OLEDs, the electroluminescence of which was close to candle emission. The best device demonstrated a very high brightness of 40 900 Cd m(-2) (at 15 V), current efficiency of 53.8 Cd A(-1) and power efficiency of 19.3 lm W-1, while the external quantum efficiency reached 18.8%. The fabricated devices demonstrated high emission characteristics even for the standard test at 1000 Cd m(-2) (current efficiency of 46.2 Cd A(-1), power efficiency of 10.6 lm W-1, EQE of 17.0%). QC 20180223

In the present work we have demonstrated double-channel emission from organic exciplexes coupled to inorganic nanoparticles. The process is demonstrated by yellow-green emission in light-emitting diodes based on organic exciplexes hybridized with perovskite-type dispersed BaZrO3 nanoparticles. Such double-channel emission provides a broadening of the electroluminescence spectrum and a resultant yellow-green emission color of the device. We have realized an energy transfer from the exciplexes arranged by the interface between two organic layers and the spherical-shaped BaZrO3 nanoparticles randomly deposited on the organic interface constructed of the tris(4-carbazoyl-9-ylphenyl)amine and 4,7-diphenyl-1,10-phenanthroline molecules. The fabricated device exhibits a current efficiency value of 3.88 C d/A, maximum brightness of 3465 cd/m2 (at 15 V), and external quantum efficiency of about 1.26%. In order to estimate the efficiency of the energy transfer from the exciplex to the BaZrO3 nanoparticles we have applied the Förster model for the dipole-dipole energy transfer accounting for the mutual overlap of the exciplex emission spectrum and the absorption spectrum of the BaZrO3 nanoparticles.

Different donor-acceptor-donor (D-A-D) and donor-π-bridge-acceptor-π-bridge-donor (D-π-A-π-D) systems based on a quinoxaline acceptor are compared. A significant difference in electrochemical and photophysical properties was found depending on molecular structure. A luminescence shift from 539 nm up to 671 nm was observed upon extension of conjugation length. The studied compounds were tested in fluorescent organic light emitting diodes (OLEDs) demonstrating an external quantum efficiency up to 4.5% for a deep red non-doped device and 7% when doped into an exciplex host device. A quantum-chemical interpretation of the electroluminescence spectra for the fabricated OLEDs was carried out including modelling of excimers and exciplexes.

Two new carbazole-containing aromatic imides were synthesized by three-step synthetic pathway with the moderate yields up to 76%. The compounds were investigated theoretically. TD-DFT computational studies revealed low singlet-triplet energy differences. The compounds were found to have relatively high thermal stability with 5% mass loss temperatures in the range of 280–310 °C. Phthalimide-based compound exhibited aggregation-induced emission enhancement and thermally activated delayed fluorescence with photoluminescence quantum efficiency of 20% in the solid state. Structure-properties relationship of this compound was investigated and it was found that charge-transfer through space mechanism is responsible for the emission. Series of green-emitting doped and non-doped electroluminescent devices were fabricated based on the carbazole-phthalimide derivative were fabricated to reveal best-performing mCP-doped device demonstrating maximum external quantum efficiency of 2.4% with current efficiency of 6.6 cd/A and power efficiency of 4.0 lm/W with maximum brightness of 8300 cd/m2.

A new interface engineering method is demonstrated for the preparation of an efficient white organic light-emitting diode (WOLED) by embedding an ultrathin layer of the novel ambipolar red emissive compound 4,4-difluoro-2,6-di(4-hexylthiopen-2-yl)-1,3,5,7,8-pentamethyl-4-bora-3a,4a-diaza-s-indacene (bThBODIPY) in the exciplex formation region. The compound shows a hole and electron mobility of 3.3 × 10-4 and 2 × 10-4 cm2 V-1 s-1, respectively, at electric fields higher than 5.3 × 105 V cm-1. The resulting WOLED exhibited a maximum luminance of 6579 cd m-2 with CIE 1931 color coordinates (0.39; 0.35). The bThBODIPY dye is also demonstrated to be an effective laser dye for a cholesteric liquid crystal (ChLC) laser. New construction of the ChLC laser, by which a flat capillary with an optically isotropic dye solution is sandwiched between two dye-free ChLC cells, provides photonic lasing at a wavelength well matched with that of a dye-doped planar ChLC cell.

New stable WOLEDs based on pi-extended azatrioxa[8]circulenes have been fabricated. Combining the own blue emission of the azatrioxa[8] circulenes with the yellow-green emission of the "m-MTDATA:azatrioxa[8]circulene'' exciplex a broad visible region, from 400 to 700 nm, is covered. The so constructed WOLEDs exhibit a luminance exceeding 23 700 cd m(-2) and an external quantum efficiency reaching 3%. QC 20170613

International audience; A new biscarbazoloanthracene consisting of nine fused aromatic rings, including two pyrrole units, has been obtained in a straightforward and convergent synthesis. Computational chemistry and conformational analysis revealed that the semiconductor's molecule is not planar, the two carbazole moieties being helical twisted from the plane of the anthracene unit. Photophysical and electrochemical measurements showed that this angular fused heteroacene has a low lying HOMO energy level with a wide band gap despite its extended π-conjugated molecular framework. Based on its relatively low-lying HOMO level, the semiconductor promises a high environmental stability in comparison to other related linear fused acenes and heteroacenes. The biscarbazoloanthracene has been applied as the light emitting layer in a white light emitting diode (WOLED). It is proposed that the white OLED feature is due to dual light emission properties from the active semiconductor layer being based on both the molecular luminescence of the small molecule and a discrete excimer emission made possible by suitable aggregates in the solid state. Noteworthy, this is the first reported example of such a behavior observed in a small molecule heteroacene rather than an oligomer or a polymer.

Star-shaped carbazole-based compounds were synthesized by the Buchwald–Hartvig method. The materials were examined by various experimental and theoretical methods, including differential scanning c...

An in-depth analysis of the electro-optical and light emissive properties was carried out with a new fused heteroacene, the bis [(1,2)(5,6)] indoloanthracene. The compound was synthesized in a straightforward bidirectional manner from 1,4-dibromo-2,5-diodobenzene utilizing a reaction cascade of isomerisation and cyclisation sequences. Bis-[(1,2)(5,6)] indoloanthracene exhibits bright luminescence with high quantum yield in solution as well as in the solid state. By using this novel semiconductor as active layer, an efficient OLED has been fabricated for which its emission pattern resembles at least two emitters in a single emissive region originated from the same molecule. One has its origin from the single molecule and is similar to the luminescence spectra in solution, whereas the other functions through the formation of aggregates being similar with the emission pattern found with crystals of bis-[(1,2)(5,6)]indoloanthracene. As a result bright sky-blue OLEDs with very high luminance exceeding 10000 cd/m2 were obtained. Such color pattern and performance has not previously been observed with low molecular weight, electron-rich fused polycyclic aromatic compounds and indicate a promising new class of materials for development.

Diphenilamino-substituted carbazoles were used as guest compounds for the preparation of highly efficient blue organic light-emitting diodes based on the phenomenon of delayed fluorescence. It was shown that the spectra of the delayed fluorescence of host–guest systems are identical to those of the prompt fluorescence and in general coincide with the photoluminescence spectra of the guest films. The congruence of the prompt and delayed fluorescence spectra is explained by the effective intermolecular triplet–singlet (T → S) energy transfer from the excited T states of the host to the S states of the guest molecules. High external electroluminescence efficiency of the fabricated electroluminescent devices, reaching 17%, is comparable to that achieved in phosphorescence-based organic light-emitting diodes.

Organic light emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) utilize molecular systems with a small energy splitting between singlet and triplet states. This can either be realized in intramolecular charge transfer states of molecules with near-orthogonal donor and acceptor moieties or in intermolecular exciplex states formed between a suitable combination of individual donor and acceptor materials. Here, we investigate 4,4'-(9H,9'H-[3,3'-bicarbazole]-9,9'-diyl)bis(3-(trifluoromethyl) benzonitrile) (pCNBCzoCF3), which shows intramolecular TADF but can also form exciplex states in combination with 4,4',4''-tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA). Orange emitting exciplex-based OLEDs additionally generate a sky-blue emission from the intramolecular emitter with an intensity that can be voltage-controlled. We apply electroluminescence detected magnetic resonance (ELDMR) to study the thermally activated spin-dependent triplet to singlet up-conversion in operating devices. Thereby, we can investigate intermediate excited states involved in OLED operation and derive the corresponding activation energy for both, intra- and intermolecular based TADF. Furthermore, we give a lower estimate for the extent of the triplet wavefunction to be >1.2 nm. Photoluminescence detected magnetic resonance (PLDMR) reveals the population of molecular triplets in optically excited thin films. Overall, our findings allow us to draw a comprehensive picture of the spin-dependent emission from intra- and intermolecular TADF OLEDs., 9 pages, 5 figures

In the current study we demonstrate an application of four previously synthesized 1,7-diphenyl-substituted BODIPY species for inverted photovoltaic cells and for organic light-emitting devices (OLEDs). Depending on the type of substituents or annulation of the pyridone rings these dyes exhibit spectral properties in the full visible region up to the near-infrared wavelengths. All the studied compounds show very strong visible absorption that can be ascribed to the low lying LUMO levels making them electronically suitable as acceptors for many donor materials. The best fabricated inverted photovoltaic device based on the BODYPI-core derivatives demonstrates a power conversion efficiency equal to 1.36% which is close to previously published reports for related species. Two kinds of deep red OLEDs (doped and undoped) with narrow electroluminescence spectra (full width at half maximum up to 45 nm) have been fabricated. Maximum brightness of 3900 cd m−2 and an external quantum efficiency by 2.3% were achieved for the best OLED structure.