Blue light-emitting diodes from 2-(10-naphthylanthracene)-spiro[fluorene-7,9′-benzofluorene] host material

A novel, spiro-type host material 2-(10-naphthylanthracene)-spiro[fluorene-7,9′-benzofluorene] was prepared by reacting 2-bromo-spiro[fluorene-7,9′-benzofluorene] with 9-(2-naphthylanthracene)-10-boronic acid via the Suzuki reaction. 2-4′-(Phenyl-4-vinylbenzeneamine)phenyl-spiro[fluorene-7,9′-benzofluorene], 4-[2-naphthyl-4′(phenyl-4-vinylbenzeneamine)]phenyl and diphenyl-[4-(2-[1,1;4,1]terphenyl-4-yl-vinyl)-phenyl]-amine were used as dopant materials. Devices with the configuration of ITO/N,N′-bis[4-(di-m-tolylamino)phenyl]-N,N′-diphenylbiphenyl-4,4′-diamine)/bis[N-(1-naphthyl)-N-phenyl]benzidine/2-(10-naphthylanthracene)-spiro[fluorene-7,9-benzofluorene]:5% dopant/aluminum tris(8-hydroxyquinoline)/Al-LiF showed a maximum power efficiency of 3.7 cd/A at 17.93 mA/cm² and a maximum luminance of 5018 cd/m² at 10 V with a turn-on voltage of 4.5 V.     

Trinuclear Ru(II) polypyridyl complexes as human telomeric quadruplex DNA stabilizers

Two new trinuclear ruthenium(II) complexes [(bpy)₆Ru₃(tpbip)]⁶⁺ (1) and [(bpy)₆Ru₃(tptaip)]⁶⁺ (2) (bpy = 2,2′-bipyridine, tpbip = 1,3,5-tris(1,10-phenanthroline-[5,6-d]imidazol-2-yl)-benzene, tptaip = 2,4,6-tri(1,10-phenanthroline-[5,6-d]imidazol-2-yl)-1,3,5-triazine) have been synthesized and characterized. The interaction of human telomeric DNA with Ru(II) complexes was explored by means of CD spectroscopy, fluorescence titration, ITC and FRET melting. Results indicated that two complexes not only induce a remarkable conformational change of human telomeric DNA, but also have the ability to stabilize the G-quadruplex.     

Novel,blue light-emitting polyfluorenes containing a fluorinated quinoxaline unit

A series of fluorinated quinoxaline containing polyfluorenes were synthesized by Suzuki polycondensation. The polymer light emitting diodes based on the resulting copolymers emitted blue light, and no green emission was observed either in the photoluminescence spectra when the film had been annealed at 80–160 °C nor in the electroluminescence spectra when the current densities increased from 5 to 200 mA cm^?2. The fluorescence quantum yields decreased from 79% to 36% with increasing content of BPFQ from 1 to 20 mol%. Peak external quantum efficiency and luminous efficiency were 2.99% and 2.39 cd A^?1, respectively, with CIE coordinates of (0.16, 0.10).     

Improved photovoltaic performances of Ru (II) complex sensitized DSSCs by co-sensitization of carbazole based chromophores

Herein, we report photovoltaic performance studies of three carbazole based dyes (N_1–3) derived from (Z)-3-(9-hexyl-9H-carbazol-3-yl)-2-(thiophen-2-yl)acrylonitrile scaffold as effective co-sensitizers in Ru (II) complex, i.e. NCSU-10 sensitized DSSCs. From the results it is evident that, the device fabricated using co-sensitizer N₃ with 0.2 mM of NCSU-10 exhibited improved photon conversion efficiency (PCE) of 8.73% with J_SC of 19.87 mA·cm^− 2, V_OC of 0.655 V and FF of 67.0%, while N₁ displayed PCE of 8.29% with J_SC of 19.75 mA·cm^− 2, V_OC of 0.671 V and FF of 62.6%, whereas NCSU-10 (0.2 mM) alone displayed PCE of 8.25% with J_SC of 20.41 mA·cm^− 2, V_OC of 0.667 V and FF of 60.6%. However, their EIS studies confirm that, N₁, showing higher V_OC is efficient in suppressing the undesired charge recombination in DSSCs through enhanced surface coverage on TiO₂ and thereby resulting in longer electron lifetime than that of NCSU-10 dye alone. Here, the higher PCE of N₃ can be attributed to its improved light harvesting efficiency, which is due to the presence of highly electron withdrawing barbituric acid in its structure. Conclusively, the results showcase the potential of simple carbazole based dyes as co-sensitizers in improving efficiency of DSSCs.     

Study on the wet processable antimony tin oxide (ATO) transparent electrode for PLEDs

A polymer light emitting diodes (PLEDs) was fabricated using the wet processable antimony tin oxide (ATO) as the transparent electrode by spin coating method. PLED were fabricated with ATO (or ITO)/PEDOT:PSS/polymer/BaF₂/Ba/Al configurations. Electrical and optical properties of ATO transparent electrode were measured. Transmittance of ATO thin film was more than 90% in the visible region, sheet resistance was 30 Ω/□ and had a strong solvent resistance. The maximum brightness and maximum efficiency of PLED device using an ATO transparent electrode was 3637 cd/m² and 1.03 cd/A, respectively.     

Novel method for synthesis of Fe core and C shell magnetic nanoparticles

Using a newly developed method, carbon-encapsulated iron (Fe) nanoparticles were synthesized by plasma due to ultrasonication in toluene. Fe core with carbon shell nanoparticles were characterized using Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM). Fe nanoparticles of diameter 7–115 nm are encapsulated by 7–8 nm thick carbon layers. There was no iron carbide formation observed between the Fe core and the carbon shell. The Fe nanoparticles have body centered cubic (bcc) crystal structure. Synthesized nanoparticles showed a saturation magnetization of 9 A m²/kg at room temperature. After thermal treatment crystalline order of the nanoparticles improved and saturation magnetization increased to 24 A m²/kg. We foresee that the carbon-encapsulated Fe nanoparticles are biologically friendly and could have potential applications in Magnetic Resonance Imaging (MRI) and photothermal cancer therapy.     

Synthesis of fluorene- and anthracene-based π-conjugated polymers and dependence of emission range and luminous efficiency on molecular weight

In the present work poly[9,9-dioctylfluorene-co-2-pentyl-9,10-bis(4-vinylphenyl)anthracene], a fluorene- and anthracene-based copolymer, is synthesized through a Heck coupling reaction. In order to synthesize polymers with high-molecular weight, DMF (P1), DMF/p-Xylene = 1/1 (P2), p-Xylene (P3), and 1,4-Dioxane (P4) are used as solvents, which are an important factor in the synthesis process. The number of average molecular weights (M_n) of the synthesized polymers P1–P4 do not differ significantly, standing at 22,309, 12,369, 29,192, and 39,464, respectively, while their weight average molecular weights (M_w) show considerable differences (i.e. 50,055; 24,042; 125,406; and 231,053). Polymers P1–P4 demonstrate little difference in the results of a thermal analysis, electrochemical analysis, UV–vis analysis, and photoluminescence (PL) spectrum measurement. With regard to electroluminescence (EL) spectrum measurement, however, P1 and P2 show main luminous peaks at 508 nm, while P3 and P4's luminous peaks are seen at 516 nm. Moreover, luminous shoulder peaks were red-shifted with increase of molecular weight of polymers from 460 to 544 nm. In this process, the luminous area is red-shifted from greenish-blue to yellowish-green. The I–V–L measurement results show that the maximum brightness of P1, P2, and P3 ranges from 164 to 303 cd/m² and their luminous efficiency is low at 0.031–0.054 cd/A. Meanwhile, the turn-on voltage of P4, having greater molecular weight, is 9.5 V, and its maximum brightness and corresponding luminous efficiency are 736 cd/m² and 0.08 cd/A, respectively, implying that the luminous efficiency of devices improves as the molecular weight becomes greater.     

Synthesis and visible light luminescence of mononuclear nine-coordinate lanthanide complexes with 2,4,6-tris(2-pyridyl)-1,3,5-triazine

Synthesis of four nine-coordinate lanthanide (III) complexes of the type, [Ln(hfaa)₃(tptz)], where Ln = La, Nd, Sm and Tb; hfaa = the anion of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione and tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine, by a new modified one pot in situ method is reported. The lanthanide ions are coordinated to three N-atoms of three 2-pyridyl units of tptz besides six O-atoms of three hfaa units. The formation of these volatile complexes is confirmed by molecular ion peak in ESI-MS, IR and NMR. The hypersensitive ⁴G_5/2, ²G_7/2 ← ⁴I_9/2 transition displays distinct band shape which is different from the band shape of known eight- and ten-coordinate complexes. The samarium and terbium complexes emit pink and green luminescence due to ⁴G_5/2 → ⁶H_j (j = 5/2, 7/2, 9/2) and ⁵D₄ → ⁷F_j (j = 3-6) transitions, respectively.     

Tunable and selective formation of micropores and mesopores in carbide-derived carbon

Pore structure of carbide-derived carbon (CDC) was tunable by chlorination of Ti(C_1−xA_x) solid–solution carbides (A = O or N). High-energy ball milling method was used to synthesize various nanocrystalline Ti(C_1−xA_x) phases. We were able to obtain specific dimension of pore volumes in the range of micropore (<2 nm) or mesopore size (2–50 nm), depending on the compositions of the precursors. The substitutional atoms and their contents effectively modify the characteristics of pores i.e., pore size, volume and their distributions. The micropore volume density, total pore volume density and specific surface area (SSA) of Ti(C_0.7O_0.3) CDCs were found 1.55 cm³/g, 1.72 cm³/g and 3100 m²/g, respectively. In contrast, Ti(C_0.5N_0.5) CDCs showed enhancement of mesopore formation with 3.34 cm³/g, 3.45 cm³/g and 522 m²/g for mesopore volume density, total pore volume density and SSA, respectively.     

UV-polymerisable,phosphorus-containing,flame-retardant surface coatings for glass fibre-reinforced epoxy composites

A vinyl phosphonic acid based flame retardant coating has been applied on the surface of a glass-fibre reinforced epoxy (GRE) composite substrate using a UV polymerisation technique. On exposure to heat the poly (vinyl phosphonic acid) (PVPA) coating thus obtained, intumesces and acts as a thermal insulator, providing active fire protection to the composite structure. Samples with ∼300 and 500 μm thick coatings were prepared. The fire performance of the coated GRE composite was studied by cone calorimetry at 35 and 50 kW/m² heat fluxes. While the sample with ∼500 μm thick coating did not ignite at both heat fluxes, the one with the ∼300 μm thick coating ignited at 50 kW/m², however the time-to-ignition was delayed from 60 s in the uncoated sample to 195 s and the peak heat release rate reduced from 572 kW/m² to 86 kW/m². The coatings did not peel off when subjected to a tape pull test and resisted cracking/debonding during an impact drop test of up to 5 J energy. However, the coatings are hydrophilic, showing significant mass loss in a water soak test. The improvement of the hydrophobicity of these coatings is a focus of our future research.     

A highly selective turn-on sensor for Hg2 + based on a phosphorescent iridium (III) complex

A highly selective phosphorescent chemosensor for Hg^2 + based on the iridium (III) complex Ir(DTBT)₂(acac) (DTBT = 2-(5-(1,2 dihydroacenaphthylen-5-yl)thiophen-2-yl)benzothiazole, acac = acetylacetone) was synthesized and characterized. Ir(DTBT)₂(acac) exhibited relatively weak fluorescenceat at about 700 nm. Ir(DTBT)₂(acac) displayed a dramatic color change from near-infrared to yellow-green with the addition of Hg^2 +. More significantly, the chemosensor performed “turn-on” phosphorescent responses toward Hg^2 +.     

Diffusion coefficients and electrical conductivities for calcium chloride aqueous solutions at 298.15 K and 310.15 K

Experimental values for mutual diffusion coefficients (interdiffusion coefficients) for CaCl₂ aqueous solutions at 298.15 K and 310.15 K, not available in the literature, were experimentally determined between 0.005 mol dm^?3 and 0.1 mol dm^?3. The measurements were performed by using a conductimetric open-ended capillary cell. Values at infinitesimal concentration, D⁰, were also obtained. These data were analysed using the Onsager–Fuoss and Gordon models. In addition, molar conductance data were measured at 310.15 K for CaCl₂ aqueous solutions at the same concentration range and the value at infinitesimal concentration determined. Afterwards, it was split into the ionic limiting values. By replacing them into the Nernst equation, diffusion coefficients at infinitesimal concentration were derived (1.335 × 10^?9 m² s^?1 and 1.659 × 10^?9 m² s^?1) at both temperatures (298.15 K and 310.15 K, respectively). They agree well with the extrapolated experimental ones (1.312 × 10^?9 m² s^?1 and 1.613 × 10^?9 m² s^?1).     

Syntheses,crystal structures and properties of dinuclear hydrido-tris(3,5-diphenylpyrazol-1-yl)borate complexes with the S―S coupled and dimerized quinoxaline-2,3-dithiolate ligand

New dinuclear complexes with the bridging S―S coupled and dimerized quinoxaline-2,3-dithiolate (dsqdt) ligand, [Tp^Ph2M(dsqdt)MTp^Ph2] (Tp^Ph2 = hydro-tris(3,5-diphenylpyrazol-1-yl)borate; M = Co, 1; M = Ni, 2; M = Mn, 3), were prepared. X-ray crystal structure studies for complexes 1–3 indicate that the dsqdt ligand forms the unique κ²-coordinated mode through S and N atoms from the same qdt unit. The absorption spectra, redox behavior and magnetic properties of the compounds are reported.     

Polyethers containing pendent 9-aryl[3,3′]bicarbazolyl fragments as hole-transporting materials for OLEDs

Electro-active polymers containing pendent 9-aryl[3,3′]bicarbazolyl fragments were synthesized and characterized. The materials were examined by various techniques including thermogravimetry, differential scanning calorimetry, UV and fluorescence spectrometry as well as electron photoemission technique. The electron photoemission spectra of the layers showed the ionization potentials of 5.2–5.5 eV. The synthesized polymers were tested as hole-transporting materials in bilayer OLEDs with Alq₃ as the emitter. The devices with polymers containing 9,9-diethylfluorenyl or p-tolyl substituted bicarbazolyl fragments exhibited the best overall performance with turn-on voltage of about 3 V, a maximum photometric efficiency of 3.6 cd/A and maximum brightness of ca. 14,000 cd/m².     

Luminescent mononuclear Pt(II) chloride complexes with C-linked 2,2′-bipyridyl tetrazole terdentate chelating ligands

Two new luminescent mononuclear Pt(II) chloride complexes possessing C-linked 2,2′-bipyridyl tetrazole terdentate chelating ligands, namely, Pt(tbpy)Cl (1) and Pt(tmbpy)Cl (2) (tbpyH = 6-(1H-tetrazol-5-yl)-2,2′-bipyridine; tmbpyH = 6-(1H-tetrazol-5-yl)-4,4′-dimethyl-2,2′-bipyridine), have been synthesized and characterized. Complex 2 adopts a distorted square-planar geometry with a mono-anionic terdentate chelate tmbpy, and it presents a zigzag head-to-tail stacking array along the a axis with alternating Pt⋯Pt separations of 3.415 and 5.469 Å. For 2, a moderately intensive broad absorption band appears at 350–425 nm in dilute DMF solution, most likely assigned as the metal-to-ligand charge transfer ¹MLCT (Pt(5d) → tmbpy) transition, mixed with some halide-to-ligand charge transfer ¹XLCT (Cl → tmbpy) and intraligand (IL) ¹ππ* transitions inside tmbpy. It is demonstrated that the solubilities and luminescence properties of 1 and 2 are markedly influenced by the substituents in the 4 and 4′-positions of the 2,2′-bipyridyl ring. The solid-state emissions of 1 and 2 are perhaps best attributable to the ³MMLCT/³XLCT/³IL states, as supported by TD-DFT calculation of 2.     

3D network-like porous MnCo2O4 by the sucrose-assisted combustion method for high-performance supercapacitors

3D network-like porous MnCo₂O₄ nanostructures have been successfully fabricated through a facile and scalable sucrose-assisted combustion route followed by calcination treatment. Benefiting from its advantages of the unique 3D network-like architectures with large specific surface area (216.15 m² g⁻¹), abundant mesoporosity (2–50 nm) and high electronic conductivity, the as-prepared MnCo₂O₄ electrode displays a high specific capacitance of 647.42 F g⁻¹ at a current density of 1 A g⁻¹, remarkable capacitance retention rate of 70.67% at current density of 10 A g⁻¹ compared with 1 A g⁻¹, and excellent cycle stability (only 6.32% loss after 3000 cycles). The excellent electrochemical performances coupled with facile and cost effective method will render the as-fabricated 3D network-like porous MnCo₂O₄ as a promising electrode material for supercapacitors.     

An unexpected oxovanadium(IV) complex with in situ generated lactone ligand: Synthesis,crystal structure and DNA-binding property

A novel unexpected oxovanadium(IV) complex, [VO(L)(Phen)] (H₂L = 2-((2-hydroxynaphthalen-1-yl)-methyleneamino)-5-oxotetrahydrofuran-2-carboxylic acid, Phen = 1, 10-phenanthroline) (1), in which the L^2– is an unexpected in situ generated lactone Schiff base ligand from the precursor of K₂HL¹ (K₂HL¹ = potassium 2-(((2-hydroxynaphthalen-1-yl)methylene)amino)pentanedioate), has been synthesized and structurally characterized. The DNA binding properties of 1 with calf thymus DNA (CT-DNA) have been investigated by fluorescence and circular dichroism (CD) spectra, results indicate that 1 can bind to CT-DNA via an intercalative mode.     

Functional derivatives of (bi)phenyl-substituted carbazoles as building blocks for electro-active polymers

(Bi)phenyl-substituted carbazoles containing reactive functional groups were synthesized by the multi-step synthetic rout. The monomers were examined by various techniques including thermogravimetry, differential scanning calorimetry, UV and fluorescence spectrometry as well as electron photoemission technique. These derivatives were also tested as hole transporting materials in bilayer OLEDs with Alq₃ as the emitter. The devices exhibited promising overall performance with a turn-on voltage of ～3 V, a maximal photometric efficiency of 5.1 cd/A and maximum brightness of 12,200–15,600 cd/m².     

Nitrogen-doped porous carbons through KOH activation with superior performance in supercapacitors

A series of nitrogen-doped porous carbons are prepared through KOH activation of a nonporous nitrogen-enriched carbon which is synthesized by pyrolysis of the polymerized ethylenediamine and carbon tetrachloride. The porosity and nitrogen content of the nitrogen-doped porous carbons depend strongly on the weight ratio of KOH/carbon. As the weight ratio of KOH/carbon increases from 0.5 to 2, the specific surface area increases from 521 to 1913 m² g⁻¹, while the nitrogen content decreases from 10.8 to 1.1 wt.%. The nitrogen-doped porous carbon prepared with a moderate KOH/carbon weight ratio of 1, which possesses a balanced specific surface area (1463 m² g⁻¹) and nitrogen content (3.3 wt.%), exhibits the largest specific capacitance of 363 F g⁻¹ at a current density of 0.1 A g⁻¹ in 1 M H₂SO₄ aqueous electrolyte, attributed to the co-contribution of double-layer capacitance and pseudocapacitance. Moreover, it shows excellent rate capability (182 F g⁻¹ remained at 20 A g⁻¹) and good cycling stability (97% capacitance retention over 5000 cycles), making it a promising electrode material for supercapacitors.     

Four new cyclometalated phenylisoquinoline-based Ir(III) complexes: Syntheses,structures, properties and DFT calculations

Four new cyclometalated phenylisoquinoline-based iridium(III) complexes [Ir(C^∧N)₂(bipy)]PF₆ (5a–5d) (bipy = 2,2′-bipyridine) have been synthesized and fully characterized, where the C^∧N ligands are 1-(4-(trifluoromethyl)phenyl)isoquinoline, 4-(isoquinolin-1-yl)benzaldehyde, 4-(isoquinolin-1-yl)benzonitrile and 1-(3-fluoro-4-methylphenyl)isoquinoline, respectively. The crystal structures of 5a and 5c have been determined. The photophysical and electrochemical properties of these new complexes 5a–5d have been studied. All Ir(III) complexes exhibit orange phosphorescence in dichloromethane solution at room temperature with a maximum at 593–618 nm, quantum yield of 0.046–0.16. The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 5a–5d have been calculated with density functional theory (DFT) and time-dependent DFT (TD-DFT).