A BODIPY-based highly emissive dye with thiophene-based branch harvesting the light

ABSTRACT

A novel BODIPY-based dye with highly emissive character was configured by Sonogashira coupling and routinely characterized by NMR and MS technology. The emission of dye was investigated in solution/film/solid and shows intensive emission. In solution, the emission peak appeared around 510 nm with little influence by the polar environment. The terthiophene plays an effective antenna effect, harvesting the light and transferring the energy to BODIPY. The pseudo Stoke's shift enlarged to ～170 nm in solution. In film, the emission peak shifted to 563 nm in polycarbonate matrix. And it shifted further to 585 nm in solid due to the highly twisted structure, which avoided closely regular-tight packing. The dye rendered an intense fluorescence, good optothermal stability, and high fluorescence quantum yield (0.55). The solid emission showed highly red emission with Commission Internationale de L'Eclairage (CIE) coordinates of (X = 0.69, Y = 0.31). Thus, the synthesized dye is idea candidate for emitting materials.     

Synthesis of the Copolymer Based on Diketopyrrolopyrrole with Didecyl Chain for OPVs

A new accepter unit, diphenylpyrrolo[3,2-b]pyrrole-2,5-dione with didecyl chain, was prepared and utilized for the synthesis of the conjugated polymer containing electron donor-acceptor pair for OPVs. The iDPP, part of the structure of a natural dye found in lichens, is the regioisomer of the known DPP with switched position of the carbonyl group and nitrogen atom. At the 4-positions of the N-substituted phenyl groups of 1,4-bis(4-butylphenyl)-pyrrolo[3,2-b]-pyrrole-2,5-dione unit in P-butyl, the butyl group was substituted with decyl group to increase solubility. The absorption spectrum of polymer with diphenylpyrrolo[3,2-b]pyrrole-2,5-dione unit exhibit two maximum peaks at about 365 and 542 nm. The spectrum of the P1 as the solid thin film shows absorption band with maximum peaks at 370 and 536 nm, and the absorption onset at 703 nm, corresponding to band gap of 1.76 eV. The oxidation and reduction potential onset of the synthesized polymer were estimated to be 0.84 and ?1.22 V, which correspond to HOMO and LUMO energy levels of ?5.64 and ?3.58 eV, respectively. The devices comprising P1 with PC₆₁BM annealed at 100°C showed a V_OC of 0.79 V, a J_SC of 1.75 mA/cm², and a FF of 0.31, leading to the power conversion efficiency of 0.43% under white light illumination (AM 1.5 G, 100 mW/cm²).     

Theoretical Design Study on the Electronic Structures and Phosphorescent Properties of Four Iridium(III) Complexes

The geometry structures, electronic structures, absorption, and phosphorescent properties of four Ir(III) complexes have been investigated using the density functional method. Calculations of ionization potential (IP) and electron affinity (EA) were used to evaluate the injection abilities of holes and electrons into these complexes. The result also indicates that the –CF₃ substituent group on the ligand not only change the character of transition but affect the rate and balance of charge transfer. The lowest energy absorption wavelengths are located at 428 nm for 1a, 446 nm for 1b, 385 nm for 2a, and 399 nm for 2b, respectively, in good agreement with the energy gap (ΔE_L-H) trend because the HOMO–LUMO transition configurations are predominantly responsible for the S₀→S₁ transition. 2b has the 433 nm blue emission, which might be a potential candidate for blue emitters in phosphorescent dopant emitters in organic light emitting diodes (OLEDs). The study could provide constructive information for designing novel OLEDs materials in the future.

[Supplemental materials are available for this article. Go to the publisher's online edition of Molecular Crystals and Liquid Crystals to view the free supplemental file.]     

Structural and magnetic properties of nanometric Zn0.5Co0.5Fe2O4 prepared by hydrothermal method

ABSTRACT

The study of the structural, morphology and magnetic properties of Zn_0.5Co_0.5Fe₂O₄ ferrite is the objective of this work. The sample was prepared by hydrothermal method and was characterized by X-ray diffraction (XRD), (SEM) and (TEM) micrographs and magnetization measurements.

The magnetic hysteresis loops, field cooling (FC) and zero field cooling (ZFC) curves, in temperature range (0-400K), were measured using XL-SQUID magnetometer and the values of blocking temperatures (T_B) were determined. The results indicated that Zn_0.5Co_0.5Fe₂O₄ sample were formed in a single spinel phase and gives the value for the lattice parameter (8.3952 Å) and nanosizes of particles (13.8 nm) were compared with these obtained from ZnFe₂O₄ sample prepared also by synthesis method (8.4261 Å and 14 nm). Although, the superparamagnetic behaviour for Co-Zn ferrite has observed at 350K with a blocking temperature (T_B = 300K), that is maximum at the value obtained in the case of Zn-ferrite (T_B = 12K).     

Intercalation of O2 and its Effect on the Properties of C60 and C70 Solids

Abstract

The intercalation of O₂ in C₆₀ and C₇₀ solids have been studied. In both gas effusion spectra of C₆₀ and C₇₀ powder exposed to O₂ at room temperature, two evolution peaks of O₂ are found near 80 and 150°C. In both C₆₀ and C₇₀ powder, the peak near 80°C does not depend on a heating ratio and the peak near 150°C shifts to higher temperature with the heating ratio. The activation energy on diffusion of O₂ in C₆₀ and C₇₀ solids are ～0.27eV and ～0.46eV, respectively. The number of O₂ intercalated in C₇₀ powder is larger than that in C₆₀ powder. Electron spin density of 02-intercalated C₆₀ film is larger than that of C₇₀ film. The effect on the properties of C₆₀ and C₇₀ solids by the intercalation of O₂ are discussed.     

Synthesis of a BDT-based small-molecule acceptor with dye end groups for organic photovoltaic cell application

ABSTRACT

An acceptor-donor-acceptor (A–D–A)-type small molecule, BDT-IN, having a benzo[1,2-b:4,5-b']dithiophene (BDT) unit as its electron-donating core (D) and an 1,3-indanedione (IN) unit as its electron-withdrawing end group (A), was synthesized by Knoevenagel condensation. The BDT-IN film showed broader UV absorption with a greater red shift (λ_max = 622 nm) than that of the BDT-IN solution (λ_max = 570 nm). The organic photovoltaic cells were fabricated with an ITO/PEDOT:PSS/poly(3-hexylthiophene): BDT-IN/LiF/Al configuration, and showed a power conversion efficiency of 0.23%.     

In Situ FT-IR Study of an Electron-Beam Induced Reaction of C60 Film

Abstract

The structural modification induced by electron-beam (EB) in a C₆₀ film and its kinetics have been studied using in situ high-resolution FT-IR spectroscopy. Similar to studies on photoirradiated K_xC₆₀ fim, was found that a coalescence reaction between adjacent C₆₀ molecules takes place. In order to investigate the interaction between an incident electron and Cgg molecules, the time-dependence of the amounts of C₆₀ on the EB irradiation was examined. It was found that the reaction rate exhibits a linear dependence on the reactant concentration and nonlinear dependence on the incident current.     

Synthesis and electroluminescent properties of new diazocine derivatives

ABSTRACT

DAPCz and DANaPCz have been successfully synthesized and characterized. DAPCz and DANaPCz in film state showed absorption in the range of 322 to 345 nm wavelength and exhibited blue photoluminescence (PL) emission peaks at 428 and 425 nm. PL wavelength of DAPCz is red-shifted by 3 nm than that of DANaPCz, which is due to the carbazole electron donating group of DAPCz. The use of DAPCz in a non-doped OLED device resulted in blue emission with current efficiency of 1.01 cd/A and C.I.E. of (0.26, 0.37).     

Efficiency Enhancement of Polymer Solar Cells with Three-Component Active Layer

The photvoltaic performance of polymer solar cell (PSC) with a three-component active layer was studied. The incorporation of 4-cyano-4’-octylbiphenyl (8CB) as an additive to a P3HT [poly(3-hexylthiophene)]:PC₆₁BM [[6,6]-phenyl-C61-butyric acid methyl ester] blend film led to a higher absorbance, larger crystal size, closer packing of P3HT, and hence enhanced hole mobility. The power conversion efficiency of the PSC with the three-component active layer (P3HT: PC₆₁BM:8CB blend film) was improved by over 30% compared to that of the reference device without 8CB, due to an enhancement in all parameters such as short circuit current, open circuit voltage and fill factor.     

Synthesis and property of diazocine derivatives substituted with imidazole in various positions

ABSTRACT

TIACA-I, TIACA-II were synthesized by changing the substitution position of the imidazole group in the diazocine core. TIACA-I, TIACA-II in the film state showed absorption in the range of 354 to 392 nm and exhibited blue photoluminescence (PL) emissions at 448 and 462 nm, respectively. The PL wavelength of TIACA-II is red-shifted by 14 nm than that of TIACA-I due to the electron-donating intensity depending on the position of the imidazole group. The use of TIACA-II in a non-doped OLED device resulted in blue emission with current efficiency of 2.84 cd/A and CIE of (0.15, 0.18).     

Synthesis and Properties of Novel Nonlinear Optical Polyester Containing Cyanovinylnitroresorcinoxy Group

Novel X-type polyester 5 containing 4-(2’-carbomethoxy-2’-cyano)vinyl-6-nitroresorcinoxy group as nonlinear optical (NLO) chromophore, which constitutes parts of the polymer backbone, was prepared and characterized. Polyester 5 is soluble in common organic solvents such as N,N-dimethylformamide and acetone. Polyester 5 shows a thermal stability up to 280°C from thermogravimetric analysis with glass-transition temperature obtained from differential scanning calorimetry of near 116°C. The second harmonic generation (SHG) coefficient (d₃₃) of poled polymer film at the 1064 nm fundamental wavelength is 4.25 × 10^?9 esu. The dipole alignment exhibits a thermal stability even at 4°C higher than glass-transition temperature (T_g), and no significant SHG decay is observed below 120°C due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.     

Synthesis and Nonlinear Optical Properties of Novel Polyurethane Containing Cyanovinylnitroresorcinoxy Group

Novel X-type polyurethane 5 containing 4-(2′-carbomethoxy-2′-cyano)vinyl-6-nitroresorcinoxy groups as nonlinear optical (NLO) chromophores, which constitute part of the polymer backbone, was prepared and characterized. Polyurethane 5 is soluble in common organic solvents such as acetone and N,N-dimethylformamide. It shows thermal stabilities up to 260°C from thermogravimetric analysis with glass transition temperature obtained from differential scanning calorimetry near 108°C. The second harmonic generation (SHG) coefficient (d₃₃) of poled polymer film at 1064 nm fundamental wavelength is 9.83 × 10^?9 esu. Polymer 5 exhibits a high thermal stability even at 2°C higher than T_g, and no significant SHG decay is observed below 110°C, which is acceptable for nonlinear optical device applications.     

Synthesis and Characterization of Violet Light Emitting Polymer based on Fluorene and Dimethylsilane

New fluorene based light emitting polymer, poly[(4-(9,9-didecyl-9H-fluoren-2-yl) phenyl)dimethyl(phenyl)silane] (PFDPS), was synthesized by palladium-catalzed Suzuki coupling reaction. The obtained copolymer was characterized by ¹H-NMR, and IR-spectroscopy. The polymer showed good solubility in common organic solvents and weight average molecular weight of 16,300 with polydispersity index of 1.4. The maximum photoluminescence of the solution and film of the polymer was observed at 392 nm and 410 nm, respectively.

The double-layered device with the configuration, ITO/PEDOT/PFDPS/LiF/Al structure has a turn-on voltage at about 5.5 V and maximum brightness of 9.40 cd/m², and emitted violet light at 414 nm.     

New Mesogenic Compounds Containing a Terminal-Substituted Benzoxazole Unit

A series of novel mesogenic 2-(4-alkoxyphenyl-1-yl)-benzoxazole derivatives bearing different substituents (H, NO₂, CH₃, Cl, coded as nPB-H, nPB-N, nPB-M, and nPB-C, respectively) at the 5-position were prepared and characterized. nPB-N, nPB-M, and nPB-C exhibited enantiotropic smectic mesophases with the mesophase ranges 3 °C–32 °C and 3 °C–82 °C on heating and cooling processes, whereas nPB-H showed no mesophases. The substituents with the stronger electron withdrawing effect let to the wider mesomorphic temperature domain. The nPB-M, nPB-C, and nPB-H displayed intense emission in CH₂Cl₂ solutions with λ_max peaks of the photoluminescence spectra at 350–355 nm when excited at their absorption maxima.     

Structures and Non-linear Optical Properties of Multi-Sulfur π-Conjugated Compounds 4,5-Vinylenedithio-1,3-dithiole-2-thione (C5H2S5) and 4,5-Vinylenedithio-1,3-dithiole-2-one (C5H2OS4)

Abstract Both the title multi-sulfur molecules C₅H₂S₅ (1) and C₅H₂OS₄ (2) have a chair conformation, while molecule 1 has a higher degree of π-conjugation. Both the crystals are characterized by short S···S intermolecular contacts and by face-to-face column-like packing style, but crystal 1 has been more stabilized which may be the result of its stronger π–π intermolecular interactions. Compound 1 crystallizes in non-centrosymmetric polar space group Pmn2₁ with a = 10.6826(17), b = 9.3633(11), c = 4.0764(6) ?, V = 407.74(10) ?³, and Z = 2. The molecular dipole moment of 1 is ±62.5(1)° away from the macro-polarization direction along the c-axis. Consequently, the crystalline powder of crystal 1 exhibit a second harmonic generating (SHG) intensity 0.5 time strong as that of urea standard powder crystals when irradiated by a 1,080 nm of Nd:YAP laser beam. Compound 2 shows no SHG effect because it crystallizes in centrosymmtric space group Pbca with a = 11.4208(8), b = 7.8843(9), c = 33.587(3) ?, V = 3024.3(5) ?³, and Z = 16. Index Abstract Structures and Non-linear Optical Properties of Multi-Sulfur π-Conjugated Compounds 4,5-Vinylenedithio-1,3-dithiole-2-thione (C₅H₂S₅) and 4,5-Vinylenedithio-1,3-dithiole-2-one (C₅H₂OS₄) Gang Xue, Qi Fang,* Wen-Tao Yu, Xia Chen, and Hong Lei Compound C₅H₂S₅ crystallizes in the polar space group Pmn2₁ and its crystalline powder exhibits a second harmonic generating (SHG) intensity 0.5 times that of urea standard (1080 nm → 540 nm), while the similar compound C₅H₂OS₄ has no SHG effect because of its centrosymmetric space group Pbca.      

X-Ray Diffraction and Physical Properties of Potassium Fullerides KxC70

Abstract

X-ray diffraction and magnetic-susceptibility measurements have been carried out for single phase K_xC₇₀ (x=1, 3, 4, 6 and 9) compounds synthesized by heating stoichiometric amount of K₉C₇₀ and C₇₀. The x-ray diffraction profiles show no structural transition down to 10K. The fairly large temperature-independent paramagnetic contribution was observed in x=3 and 4. The electrical resistivity has been measured for K evaporated C₇₀ film with increasing K thickness. Two resistivity minima were observed at x=1 and 4.     

Study of the surface state density and potential in MIS diode Schottky using the surface photovoltage method

ABSTRACT

The effects of surface preparation and illumination on electric parameters of Au/GaN/GaAs Schottky diode were investigated. The thin GaN film is realized by nitridation of GaAs substrates with different thicknesses of GaN layers (0.7 – 2.2 nm). In order to study the electrical characteristics under illumination, we use an He-Ne laser of 632 nm wavelength. The I(V) current- voltage, the surface photovltage SPV measurement were plotted and analysed taking into consideration the influence of charge exchange between a continuum of the surface states and the semiconductor. The barrier height Ф_Bn, the serial resistance R_s and the ideality factor n are respectively equal to 0.66 eV, 1980 Ω, 2.75 under dark and to 0.65 eV, 1160 Ω, 2.74 under illumination for simple 1 (GaN theckness of 0.7 nm). The interface states density N_ss in the gap and the excess of concentration δn are determined by fitting the experimental curves of the surface photovltage SPV with the theoretical ones and are equal to 4.5×10¹² eV^?1 cm^?2, 5×10⁷ cm^?3, respectively, for sample 1 and 3.5×10¹² eV^?1 cm^?2, 7×10⁸ cm^?3 for sample 2 (GaN theckness of 2 nm). The results confirm that the surface photovoltage is an efficient method for optical and electrical characterizations.     

Synthesis and light-emitting properties of a carbazole-containing hyperbranched conjugated poly(phenylene vinylene)

Abstract

A new carbazole-containing hyperbranched conjugated poly(phenylene vinylene) (Hyper-PCPPV) was synthesized through the Wittig polycondensation polymerization. Hyper-PCPPV has good solubility in common organic solvents and showed excellent thermal stability up to 425?°C with less than 5% weight loss. The photophysical properties of Hyper-PCPPV were investigated and compared with a carbazole-containing linear conjugated poly(para-phenylene vinylene) (Linear-PCPPV). An absorption maximum of Hyper-PCPPV film was determined at 353?nm which was far blue shifted than that of Linear-PCPPV (403?nm). Hyper-PCPPV showed blue photoluminescence (PL) peak at 448?nm. In addition, Hyper-PCPPV exhibited almost no excimer or aggregate emission peaks even when the polymer film was annealed at 80?°C for 30?min in air condition.     

Synthesis, Structure and Characterization of Two 1D Chain-like Cadmium Terephthalate Complexes: [Cd(tp)(H2O)3]?·?4H2O and [Ph4P][Cd(tp)0.5Cl2]?·?H2O

Abstract  Two new compounds, [Cd(tp)(H₂O)₃] · 4H₂O (1) and [Ph₄P][Cd (tp)_0.5Cl₂] · H₂O (2) (tp = terephthalate, [Ph₄P] = tetraphenylphosphonium), are metal-polycarboxylate coordination polymers prepared by similar hydrothermal synthesis techniques. Both compounds crystallize in the 1D chain-like architectures. 1 (C₈H₁₈CdO₁₁) is orthorhombic Pcca, Z = 4 (a = 7.3018(1) ?, b = 9.9975(3) ?, c = 19.9695(5) ?, V = 1457.77(6) ?³). 2 (C₂₈H₂₄CdCl₂O₃P) is triclinic P−1, Z = 2 (a = 9.5028(4) ?, b = 12.3130(5) ?, c = 12.7343(6) ?, α = 68.380(1)°, β = 73.723(1)°, γ = 89.624(1)°, V = 1321.8(1) ?³). Transition metal cadmium centers bridged by rigid linear tp ligands give rise to a 1D infinite zigzag chain polymer for 1 and a simple 1D infinite stepped chain polymer for 2. 1 presents an interesting plywood-like packing network while 2 shows a simple parallel rod-like stacking network. An intense fluorescent emission at 412 nm (λ_exc = 338 nm) for 1 in the solid state at room temperature is observed. Index Abstract  Polymeric compounds [Cd(tp)(H₂O)₃] · 4H₂O (1) and [Ph₄P][Cd (tp)_0.5Cl₂] · H₂O (2) crystallize in two remarkable 1D chain-like architectures prepared by similar hydrothermal synthesis techniques, showing an interesting plywood-like packing network in 1 and a simple parallel rod-like stacking network in 2, respectively. An intense fluorescent emission at 412 nm (λ_exc = 338 nm) for 1 in the solid state at room temperature is observed.      

Synthesis and characterization of new nematic liquid crystalline compounds-based thiophene units

Four new liquid crystalline thiophene compounds (M1?M4) with a long flexible spacer were prepared. Their structures were characterized by Fourier transform infrared and proton nuclear magnetic resonance. The mesomorphism and thermal stability were investigated with differential scanning calorimetry, polarizing optical microscopy, and thermogravimetric analysis. The photo-physical properties were evaluated using ultraviolet/visible spectroscopy and photoluminescence. M1?M4 all showed thermotropic mesogenic properties with excellent thermal stability, and exhibited nematic threaded texture, droplet texture, and Schlieren texture on heating and cooling cycles. The effect of flexible spacer and terminal groups on mesomorphic and spectroscopic property is discussed. The experimental results demonstrated that the tendency toward melting temperature (Tm) decreased, while isotropic temperature (Ti) increased with increasing the flexible spacer length. In CHCl₃ solution, these thiophene compounds displayed an intense broad absorption band peaking within 230–340 nm and a maximum fluorescent emission wavelength at 426–439 nm.