Synthesis and properties of novel hole-transporting materials with triphenylamine units

Two novel organic hole-transporting materials have been synthesized by combination of triphenylamines(TPA) viaπ-conjugated bonds using Wittig reaction.The structures were characterized by NMR,FT-IR and HRMS.The optical,electrochemical and thermal properties of the materials were studied in detail.The results show that these two compounds have blue emission,proper HOMO levels and high thermal stability.Furthermore,a quantum chemical calculation on electron distribution of the two compounds was performed, which suggests the current synthesized materials would be promising candidates for hole-transporting materials.     

Triphenylamine and quinoline-containing polyfluorene for blue light-emitting diodes

A novel blue light-emitting polyfluorene-based copolymer PTHD containing electron-rich triphenylamine and electron-poor phenylquinoline side chains in the C-9 position of fluorene unit is described. By comparison of the solution and thin film photoluminescence (PL) spectra of PTHD, a considerable red-shift of Δλ = 10-15 nm was observed in the thin film PL spectrum. The emission intensity of the shoulder peak appeared in dilute solution was also significantly enhanced in the thin film. In contrast to the reference polymer poly{[9,9-dihexylfluorene]-alt-[9,9-di(2,4-diphenylquinoline)fluorene]}, PTHD exhibits higher HOMO energy level, and higher maximum brightness with the PLED device configuration of ITO/PEDOT:PSS/polymer_70% + PBD_30%/TPBI/LiF/Al.     

Synthesis and characterization of high Tg carbazole-based amorphous hole-transporting materials for organic light-emitting devices

Novel hole-transporting materials based on carbazole dendrimers, namely G1CBC and G2CBC were synthesized and characterized. They are thermally stable with high glass transition temperatures (T_g) up to 245 °C and exhibit chemically-stable redox processes. Double-layer green OLEDs using these materials as the hole-transporting layer (HTL) with the device configuration of ITO/HTL/Alq3/LiF:Al emit brightly (λ_em 522-534 nm) from the Alq3 layer with a maximum luminance and low turn-on voltage of 15,890 cd/m² and 3.0 V, respectively. Their ability as HTLs in terms of device performance is comparable to the common hole-transporter N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB), however their thermal properties were far greater than both NPB and N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine (TPD).     

Synthesis and characterization of deep blue emitters from starburst carbazole/fluorene compounds

A series of well-defined, highly fluorescent starburst compounds with a carbazole core and oligo(2,7-fluorene ethynylene) arms have been synthesized by Sonogashira coupling reaction and fully characterized. These conjugated compounds exhibit good solubility, high thermal stability, and excellent fluorescence quantum yields (up to 0.99). The incorporation of carbazole core interrupted the main-chain conjugation and resulted in blue-shifted absorption and emission. Moreover, deep blue light has been approached from organic light-emitting diodes (OLEDs) adopting these compounds as emitting layer.     

Synthesis and characterization of 9,10-substituted anthracene derivatives as blue light-emitting and hole-transporting materials for electroluminescent devices

New 9,10-substituted anthracene derivatives were designed and synthesized for application as blue-emitting and hole-transporting materials in electroluminescent devices. They were characterized by H NMR, C NMR, FTIR, UV–vis, PL spectroscopy, and mass spectrometry. The theoretical calculation of three-dimensional structure and the energy densities of HOMO and LUMO states, as well as optical properties of these new obtained materials, supported the claim that they had non-coplanar structures. Their optical, thermal, and electrochemical properties could be tuned by varying the peripheral substituents. All of them were electrochemically and thermally stable molecules. Materials having electron donating triphenylamine as peripheral substituents showed promising potential as both blue light-emitting materials and hole-transporting materials for electroluminescent devices. Efficient blue and Alq3-based green OLEDs with maximum luminance efficiencies and CIE coordinates of 1.65 cd/A and (0.15, 0.16) and 6.25 cd/A and (0.26, 0.49) were achieved, respectively.     

Synthesis and characterization of polyfluorenes containing bisphenazine units

Novel conjugated copolymers based on 9,9‐dioctylfluorene and bisphenazine (BP) were synthesized by Suzuki polymerization. Energy transfer from the conjugated main chain to the BP moieties was observed. Full energy transfer was achieved when the molar content of the bisphenazine was 20% (20BPPF) in toluene solution. The similar phenomena were observed even for 1% bisphenazine content copolymer (1BPPF) in film. The lowest occupied molecular orbital (LUMO) energy levels (?3.06 eV) of the copolymers were lower than that of the polyfluorene homopolymer (PFO; ?2.65 eV), indicating that the introduction of the BP unit was benefit to electron injection. Single‐layer electroluminescent devices (ITO/PEDOT:PSS/polymer/LiF/Al) were fabricated to investigate their electroluminescence (EL) performances. The maximum brightness and current efficiency of all BPPF copolymers surpassed the PFO homopolymer. The best single‐layer device was based on 5BPPF, with a maximum brightness of 1532 cd/m² and current efficiency of 1.09 cd/A. Much higher efficiency could be achieved for multilayer EL devices of 5BPPF (ITO/PEDOT:PSS/PVK/polymer/TPBI/LiF/Al), which showed a maximum current efficiency of 10.01 cd/A. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1990–1999, 2010     

Nanosized starlike molecules. Synthesis and optical properties of tris- and tetrakis[oligo(disilanylenebithienylene)dimethylsilyl]benzene

The syntheses of two types of starlike molecules with the arms that extend to three and four directions have been reported. The molecules with the arms consisting of a regular alternating arrangement of a silicon-silicon bond and bithienylene unit that extend to three directions were synthesized by the reactions of 1,3,5-tris(chlorodimethylsilyl)benzene, which was chosen as a core, with the lithio[oligo(disilanylenebithienylene)] derivatives. The starlike molecules with extended arms to four directions were prepared by the reaction of 1,2,4,5-tetrakis(fluorodimethylsilyl)benzene used as a core, with lithio[oligo(disilanylenebithienylene)]s. UV-Vis absorption and fluorescence properties of these starlike molecules have been investigated in a dioxane solution. The present molecules showed absorption maxima in a range of 321-337 nm, and revealed higher fluorescence quantum yields than that of the corresponding linear polymer, poly[(tetraethyldisilanylene)bithiophene].     

Novel fluorescent N,O-chelated fluorine-boron benzamide complexes containing thiadiazoles: Synthesis and fluorescence characteristics

A series of N-(5-phenyl-1,3,4-thiadiazol-2-yl)benzamide derivatives and their corresponding BF₂ complexes were synthesized, and their photophysical properties were determined. The effect of the derivatives with various substituents on the benzamide ring and phenyl-1, 3, 4-thiadiazole ring were examined in different organic solvents and in the solid state. These dyes enjoy a series of excellent photophysical properties including the large Stokes shift, solid-state fluorescence, and aggregation-induced emission effect (AIEE).     

Synthesis and characterization of highly soluble fluorescent main chain copolyimides containing perylene units

A series of high molecular weight copolyimides containing various amount of perylene units in the main chain have been synthesized. The polymers were characterized by FT-IR, NMR, UV/Vis, fluorescence spectroscopy, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis measurements. They are highly soluble in conventional solvents such as CHCl₃, THF, cyclohexanone etc. and form optically transparent films by solution casting or spin coating. The incorporation of various amount of perylene units in the main chain allows the control of the fluorescence intensity in solution and in solid thin films. The copolyimide containing 0.28 mol% perylene units exhibits the highest solid-state fluorescence. The observed fluorescence intensities of the copolyimides in solid state film decreased with the increasing amount of perylene units in the main chain when the mole ratio of perylene units greater than 0.28 mol% indicating the aggregation of chromophores. The copolyimides are thermally stable up to 400 °C and exhibit glass transition temperatures in the range of 340-360 °C. The number average molecule weight ranges from 1.72×10⁴ to 1.25×10⁵ and the molecule weight distribution mediated between 1.9 and 2.4.     

Synthesis and characterization of polyimides containing heterocyclic units

Five new polyimides containing phenoxaphosphine as well as dibenzothiophene, phenoxathiin, and thianthrene units have been synthesized from 10-phenylphenoxaphosphine-2,3,7,8-tetracarboxylic dianhydride-10-oxide and heterocyclic diamines by the cyclopolycondensation method. These polyimides had inherent viscosities in the 0.75–1.10 dL/g range in conc. H₂SO₄ at 30°C. All the polymers were characterized by elemental analysis, density, solubility, crystallinity, IR spectra, and thermal methods.     

Synthesis and characterization of poly(1,4-phenylenevinylene-alt-2,5-thienylenevinylene) derivatives for organic light-emitting diodes

A new series of alternating copolymers composed of 1,4-phenylenevinylene and 2,5-thienylenylvinylene repeating units with various side chain substituents were synthesized via the Heck coupling reaction for use in light-emitting diodes (LEDs). The resulting copolymers were characterized using ¹H- and ¹³C-NMR, DSC, and TGA. These polymers were found to be soluble in common organic solvents and are easily spin-coated onto glass substrates, producing high optical quality thin films without defects. The electro-optical properties of ITO/PEDOT/Polymer/Al devices were investigated using UV-VIS, PL and EL spectroscopy. The turn-on voltages of these devices were found to be in the range 4-16 V, with a maximum brightness of about 2900 cd/m² at 12 V.     

Synthesis and characterization of cyclometalated iridium(III) complexes containing pyrimidine-based ligands

New pyrimidine derivatives (pyr) have been synthesized using palladium-catalyzed Suzuki coupling reaction. These compounds can undergo cyclometalation with iridium trichloride to form bis-cyclometalated iridium complexes, (pyr)₂Ir(acac) (acac = acetylacetonate; pyr = cyclometalated pyr). The substituents at the both cyclometalated phenyl ring and pyrimidine ring were found to affect both electrochemical and photophysical properties of the complexes. Computation results on these complexes are consistent with the electrochemical and photophysical data. The complexes are green-emitting with good solution quantum yields at ∼0.30. Light-emitting devices using these complexes as dopants were fabricated, and the device performance at 100 mA/cm² are moderate: 9 (17 481 cd/m², 4.8%, 18 cd/A, 5.1 lm/W); 10 (18 704 cd/m², 4.9%, 18.9 cd/A, 4.7 lm/W); 13 (20 942 cd/m², 5.4%, 21.0 cd/A, 6.1 lm/W).     

Synthesis and characterization of blue light-emitting poly(aryl ether)s containing pyrimidine-incorporated oligofluorene pendants with bipolar feature

Novel blue light-emitting poly(aryl ether)s comprising of bipolar oligofluorene pendants as chromophores have been designed and synthesized,in which pyrimidine and arylamine moieties are utilized as the electron acceptor and electron donor,respectively.Through varying π bridge length from monofluorene to bifluorene and end-cappers from hydrogen to carbazole and diphenylamine,the emission color of the resulting polymers covers from deep blue to greenish blue,and their HOMO and LUMO levels can be modulated to facilitate charge injection to improve the device performance.Polymer lightemitting diodes(PLEDs) are fabricated with the device structure of ITO/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid)(PEDOT:PSS)(50 nm)/polymer(80 nm)/Ca(10 nm)/Al(200 nm).Among these polymers,P2Cz5F-Py with bifluorene bridge and carbazole end-capper shows excellent trade-off between the efficiency and emission wavelength,having a peak luminous efficiency as high as 1.26 cd/A and Commission Internationale de L’Eclairage(CIE) coordinates of(0.17,0.17).     

Synthesis and properties of a luminescent organic material with triphenylamine and pentiptycene units

A donor–bridge–donor compound for blue light-emitting with triphenylamine as donor and pentiptycene derivative units as bridge was synthesized via Sonogashira reaction. The chemical structure was confirmed by NMR and MALDI-TOF MS. It emits blue light peaked at 442 nm with a FWHM of 59 nm in CH2Cl2. Fluorescent quantum efficiency in THF is 82% relative to 9,10- diphenylanthracene. A slight hypsochromic shift was found in its drop-cast film. Cyclic voltammetry revealed that it has high HOMO level corresponding to hole transporting character.     

Synthesis and characterization of polyamides containing heterocyclic thiaxanthone units

Novel polyamides containing heterocyclic thiaxanthone units were prepared by condensing 2,7-dichloroformylthiaxanthone-5,5′-dioxide and 2,8-dichloroformylthiaxanthone-5,5′-dioxide with various aromatic diamines, under low temperature solution polymerization conditions in DMAc. The model diamide, 2,8-ditolylcarbamylthiaxanthone-5,5′-dioxide was synthesised and characterized by spectroscopic methods. The polyamides were prepared in 70–80% yield and had inherent viscosity in the 0.36–0.73 dL/g range. The poyamides have decomposition temperatures in the 425–510°C range in nitrogen. The effect of thiaxanthone rings on polymer backbone on solubility, crystallinity, and thermal stability is also discussed.     

Synthesis and characterization of polyesters containing heterocyclic thiaxanthone units

Several polyesters containing thiaxanthone rings were prepared from 2,7-dichloroformylthiaxanthone-5,5′-dioxide ( IVa ), 2,8-dichloroformylthiaxanthone-5,5′-dioxide ( IVb ), and bisphenols by solution polycondensation. The 2,8-diethoxycarbonylthiaxanthone-5,5′-dioxide ( V ) was prepared and characterized by spectral methods to confirm the formation of 2,8-thiaxanthonedicarboxylic acid-5,5′-dioxide ( IVb ). Prior to polymer synthesis two model compounds,2,7-diphenoxycarbonylthiaxanthone-5,5′-dioxide (MDE-1) and 2,8-diphenoxycarbonylthiaxanthone-5,5′-dioxide (MDE-2), were synthesized and characterized by spectral methods. The polyesters were obtained in 62–78% yield and had inherent viscosities in the range 0.42–0.90 dL/g. The effect of thiaxanthone rings on solubility, crystallinity, and thermal stability of the polyesters are also discussed. The polyesters have decomposition temperatures in the range 372–438°C.     

Synthesis and characterization of alternating copolymers containing triphenylamine as hole‐transporting units

A series of light‐emitting poly(p‐phenylene vinylene)s with triphenylamine units as hole‐transporting moieties in the main chain were synthesized via Wittig condensation in good yields. The newly formed vinylene double bonds possessed a trans configuration, which was confirmed by Fourier transform infrared and NMR spectroscopy. The high glass‐transition temperature (83–155 °C) and high decomposition temperature (>300 °C) suggested that the resulting copolymers possessed high thermal stability. These copolymers, especially TAAPV1, possessed a high weight‐average molecular weight (47,144) and a low polydispersity index (1.55). All the copolymers could be dissolved in common organic solvents, such as tetrahydrofuran (THF), CHCl₃, CH₂Cl₂, and toluene, and exhibited intense photoluminescence in THF (the emission maxima were located from 478 to 535 nm) and in film (from 478 to 578 nm). The low onsets of the oxidation potential (0.6–0.75 V) suggested that the alternating copolymers possessed a good hole‐transporting property due to the incorporation of triphenylamine moieties. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3278–3286, 2001     

Synthesis, characterization, physical properties, and applications of highly fluorescent pyrene-functionalized 9,9-bis(4-diarylaminophenyl)fluorene in organic light-emitting diodes

A new, highly fluorescent pyrene-functionalized 9,9-bis(4-diarylaminophenyl)fluorene, namely PTF, was synthesized and characterized. This material is an amorphous molecular glass with notably high T_g, is electrochemically stable, and exhibits strong blue emission both in solution and solid state. It shows promising ability as a solution processed blue emitter and hole-transporter for OLEDs. High-efficiency sky-blue and Alq3-based green devices with luminance efficiencies of 1.13 and 4.08 cd/A are achieved, respectively.     

Synthesis and characterization of side-chain liquid-crystalline polysiloxanes containing fluorinated units

Several new chiral side-chain LC polysiloxanes (IP–VIIP) bearing fluorinated methyl groups were synthesized with a cholesteric LC monomer and a non-LC monomer containing fluorinated units. The chemical structures and LC properties of the monomers and polymers were characterized by use of various experimental techniques. The effect of copolymer composition on mesomorphic properties of the fluorine-containing polymers was studied as well. The obtained polymers were soluble in many solvents and the specific rotations showed negative values. The temperatures at which 5% weight loss occurred (T _d) were greater than 300 °C for all the polymers and the residue weight on heating to 600 °C increased slightly with increase of the monomer containing fluorinated units in the polymer systems. All the polymers displayed two-phase transitions when they were heated and cooled. The IP, IIP, and IIIP exhibited cholesteric textures when they were heated and cooled, while IVP, VP, VIP, and VIIP showed smectic fan-shaped textures. XRD curves of samples of IVP, VP, VIP, and VIIP displayed sharp and strong peaks at low angle, but no sharp peaks were shown at low angle for the samples IP, IIP, and IIIP.