Oxygen-sensing properties of ormosil hybrid materials doped with ruthenium(II) complexes via a sol-gel process

Organically modified silicate (ormosil) materials doped with [4,4′-dimethyl-2,2′-bipyridine-bis(2,2′-bipyridine)] ruthenium(II) dichloride ([Ru-mbpy]²⁺) and [4,4′-dimethylformate-2,2′-bipyridine-bis(2,2′-bipyridine)] ruthenium(II) dichloride ([Ru-dmfbpy]²⁺) were prepared by a sol-gel procedure for oxygen-sensing applications. The results indicated that the concentrations of the Ru(II) diimine complexes obviously influenced the linearity of Stern-Volmer plots (I₀ /I vs. O₂%). The best suitable concentrations of [Ru-mbpy]²⁺ and [Ru-dmfbpy]²⁺ in the sol for oxygen sensors were found to be 1.0 × 10^− 3 M and 2.5 × 10^− 3 M, respectively. The fluorescence quenching time and recovery time of oxygen sensor doped with [Ru-mbpy]²⁺ (1.0 × 10^− 3 M) were 18 s and 38 s and those doped with [Ru-dmfbpy]²⁺ (1.0 × 10^− 3 M) were 13 s and 32 s, respectively. The oxygen sensor based on Ru(II) complex modified by esterification demonstrated excellent linear calibration relationship and improved long-term stability.     

Efficient and Stable Solid‐State Dye‐Sensitized Solar Cells Based on a High‐Molar‐Extinction‐Coefficient Sensitizer

The high‐molar‐extinction‐coefficient heteroleptic ruthenium dye, cis‐Ru (4,4′‐bis(5‐octylthieno[3,2‐b] thiophen‐2‐yl)‐2,2′‐bipyridine) (4,4′‐dicarboxyl‐2,2′‐bipyridine) (NCS)₂, exhibits an AM 1.5 solar (100 mW cm^?2)‐to‐electric power‐conversion efficiency of 4.6% in a solid‐state dye‐sensitized solar cell (SSDSC) with 2,2′, 7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenylamine)9,9′‐spirobifluorene (spiro‐MeOTAD) as the organic hole‐transporting material. These SSDSC devices exhibit good durability during accelerated tests under visible‐light soaking for 1000 h at 60 °C. This demonstration elucidates a class of photovoltaic devices with potential for stable and low‐cost power generation. The electron recombination dynamics and charge collection that take place at the dye‐sensitized heterojunction are studied by means of impedance and transient photovoltage decay techniques.     

Stable, high-efficiency ionic-liquid-based mesoscopic dye-sensitized solar cells

Efficient and stable mesoscopic dye-sensitized solar cells (DSCs) introducing a low-viscosity binary ionic liquid (1-propyl-3-methyl-imidazolium iodide (PMII) and 1-ethyl-3-methyl-imidazolium tetracyanoborate (EMIB(CN)(4))) electrolyte in combination with a new high-molar-extinction-coefficient ruthenium complex, Ru(2,2'-bipyridine-4,4'-dicarboxylic acid)(4,4'-bis(2-(4-tert-butyloxy -phenyl)ethenyl) -2,2'-bipyridine) (NCS)(2), are demonstrated. The dependence of photovoltaic performance, charge transport and electron lifetime on the composition of the binary ionic-liquid electrolyte with different ratios of PMII/EMIB(CN)(4) were investigated by electrochemical impedance and photovoltage transient techniques. A photovoltaic conversion efficiency of 7.6 % was obtained under simulated full sunlight illumination, which is a record for solvent-free DSCs. These devices exhibit excellent stability at 80 degrees C in the dark or under visible-light soaking at 60 degrees C during 1000 h of accelerated tests.     

Influence of donor moiety in ruthenium sensitizers on the properties of dye-sensitized solar cells

Heteroleptic ruthenium complexes cis-[Ru(H2dcbpy)(L)(NCS)2], where H2dcbpy is 4,4'-dicarboxylic acid-2,2'-bipyridine and L is 4-(4-(N,N-di-(p-hexyloxyphenyl)-amino)styryl)-4'-methyl-2,2'-bipyridine (Rut-A) or 4-(4'-(3,6-dihexyloxycarbazole-9-yl)-styryl)-4'-methyl-2,2'-bipyridine (Rut-B), have been synthesized and characterized by NMR, UV-Vis spectroscopy, and cyclic voltammogram. The effect of different electron donors on the properties of dye-sensitized solar cells has been studied. The power conversion efficiency of DSSC based on Rut-B is 6.1% while Rut-A delivered a lower efficiency of 4.52% under the same device fabrication and measuring conditions. The better photovoltaic performance of Rut-B is mainly associated with enhanced dye absorptivity and charge recombination suppression.     

Photo-electrochemistry at polymer/semiconductor interface Characterization of surface modified CdS based photovoltaic cells

The photoelectrochemical (photovoltaic and photocatalytic) properties of single crystal CdS electrodes modified with polymeric films of Ru(v-bpy)₃]²⁺ (v-bpy is 4-vinyl-4-methyl-2,2-bipyridine) are presented. Such modified electrodes exhibit longer lifetimes than their native counterparts when operated in a photovoltaic cell with the free and immobilized ferro/ferri cyanide redox system. The photocatalytic behavior with I₃ ^–/I^– with and without sulfite solution has also been investigated.     

Highly efficient dye sensitized solar cells based on a novel ruthenium sensitizer

A new sensitizer, Ru(2,2′-bipyridine-4,4′-dicarboxylic acid)-4,4′-bis(2-(4-N,N′-diphenylaminophenyl)ethenyl)-2,2′-bipyridine) (NCS)₂, denoted K77-7, was synthesized. The UV–vis spectrum of K77-7 was characterized. Dye sensitized solar cells (DSSC) based on K77-7 were fabricated and devices J/V curves were measured. The effects of co-adsorbent chenodeoxycholic acid, solvent in electrolyte, TiO₂ light scattering layer, and treatment of TiCl₄ aqueous solution on device efficiency were discussed. Under solar illumination of 100 mW cm^?2 (A.M. 1.5), the optimized DSSC device efficiency of 10.1 % was obtained.     

Novel heteroleptic ruthenium (II) complex with DPBPZ derivative for dye-sensitized solar cells

Herein, as Ru(II) complex for the dye-sensitized solar cells (DSSCs), we designed and investigated a novel heteroleptic ruthenium complex [Ru(dcbpy)(dpbpz)(NCS)2] with dpbpz derivative to enhance photovoltaic performance. The density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were used to gain insight into the factors responsible for photovoltaic properties as dye sensitizer. Molecular orbitals analysis confirmed that HOMO of [Ru(dcbpy)2(NCS)2] and [Ru(dcbpy)(dpbpz)(NCS)2] are delocalized over the ruthenium t2g character with sizable contribution from the NCS ligand orbitals. The LUMO of [Ru(dcbpy)2(NCS)2] is localized over the dcbpy moiety. However, LUMO of [Ru(dcbpy)(dpbpz)(NCS)2] is localized over the dpbpz moiety and LUMO + 1 is localized the dcbpy moiety. Overall, the absorption spectrum of the present Ru complex was more broad than that of [Ru(dcbpy)2(NCS)2] known as N3 dye. Especially, absorption band in the region between 500 nm and 600 nm was red-shifted. Moreover, the distance between the HOMO of [Ru(dcbpy)(dpbpz)(NCS)2] and the anchoring moiety is longer than that of [Ru(dcbpy)2(NCS)2]. This means that [Ru(dcbpy)(dpbpz)(NCS)2] have longer charge-separated lifetime than [Ru(dcbpy)2(NCS)2. These results are attributed to the extended pi-conjugation of dpbpz moiety. Therefore, we suggest that newly designed [Ru(dcbpy)(dpbpz)(NCS)2] heteroleptic ruthenium complex would be a good candidate as a dye sensitizer of DSSCs, comparable to [Ru(dcbpy)2(NCS)2].     

Electrospinning preparation and characterization of a new kind of composite nanomaterials: One-dimensional composite nanofibers doped with TiO2 nanoparticles and Ru(II) complex

One-dimensional composite nanomaterials, PVP (poly(vinylpyrrolidone)) fibers with diameters in the range of 300–500 nm doped with RuL₂(NCS)₂ (L = 4,4′-Dicarboxy-2,2′-bipyridine) complex and TiO₂ nanoparticles (NPs), were prepared by electrospinning technique. The morphology of the composite nanofibers was systemically studied when the diameters of TiO₂ NPs, the concentrations of TiO₂ NPs and RuL₂(NCS)₂ in the PVP matrix were changed. A new kind of organic–inorganic composite nanomaterials which combine the advantages of one-dimensional nanostructures, organic materials and inorganic materials was obtained and it is desirable for low-weight and flexible photovoltaic devices, especially for dye-sensitized TiO₂ solar cells.     

Enhanced photocurrent production by photosystem I with modified viologen derivatives

This paper describes the construction of a photogenerated electron transfer system based on photosystem I (PSI) and modified molecular wires. Gold electrode surfaces were functionalized with sodium 3-mercapto-1-propanesulfonate and the 2,2′-dimethyl-4,4′-bipyridine cation to form a self-assembled monolayer, which enabled the subsequent immobilization of PSI. A higher photocurrent was observed in the presence of sodium ascorbate as an electron donor under irradiation at 680 nm.     

New two- and three-dimensional [Cd(CN)2]n frameworks formed with cadmium cyanide and 2,2'–bipyridine and 4,4'–bipyridine

The two cadmium cyanide complexes Cd(CN)₂ (4,4'–bipy)_0.5 (1) and [Cd(2,2'–bipy)(CN)₂]₃·H₂O (2) show infinite 3D and 2D [Cd(CN)₂]_n framework structures, respectively. The cadmium cyanide framework in 1 is topologically the same as the cristobalite-like [Cd(CN)₂]_n framework but is severely distorted. A 4,4'–bipyridine molecule is trapped in each ‘supercage’ which is formed from two adjacent adamantane-like cadmium cyanide cages. In 2, the bidentate 2,2'–bipyridine ligands are coordinated to cadmium centers to prevent expansion of the 2D cadmium cyanide framework into a 3D framework.     

Silica-[Fe(bpy)3] composite particles with photo-responsive change of color and magnetic property

Photo-induced complex formation of tris-2,2′-bipyridine iron(II) complex ([Fe(bpy)₃]²⁺) from the mixture of FeCl₃ and 2,2′-bipyridine was achieved in silica gel containing 150-300 μm silica particles, derived from a complex emulsion with HCl aqueous solution and tetraethyl orthosilicate (TEOS). More than 95% of Fe(III) and 2,2′-bipyridine were incorporated in silica particles. Yellow-red color change, due to [Fe(bpy)₃]²⁺, was observed by irradiation with 365 nm UV beam at 0.3 mW cm⁻² for 120 s. The complex formation accompanies simultaneous spin transition from the high-spin state of Fe(III) to the low-spin state of Fe(II).     

Sandwiched Electrochemiluminescent Peptide Biosensor for the Detection of Prognostic Indicator in Early‐Stage Cancer Based on Hollow,Magnetic, and Self‐Enhanced Nanosheets

Currently, peptide‐based protein‐recognition has been recognized as an effective and promising approach for protein assays. However, sandwiched peptide‐based biosensor with high sensitivity and low background has not been proposed before. Herein, a sandwiched electrochemiluminescence (ECL) peptide‐based biosensor is constructed for Cyclin A₂ (CA2), a prognostic indicator in early stage of multiple cancers, based on nanosheets with hollow, magnetic, and ECL self‐enhanced properties. First, hollow and magnetic manganese oxide nanocrystals (H‐Mn₃O₄) are synthesized using triblock copolymeric micelles with core–shell–corona architecture as templates. Then, polyethyleneimine (PEI) and the composite of platinum nanoparticles and tris (4,4′‐dicarboxylicacid‐2,2′‐bipyridyl) ruthenium (II) (PtNPs–Ru) are immobilized on H‐Mn₃O₄ to form H‐Mn₃O₄–PEI–PtNPs–Ru nanocomposite, in which PEI as coreactant can effectively enhance the luminous efficiency and PtNPs as nanochannels can greatly accelerate the electron transfer. Finally, due to the coordination between Eu³⁺ and carboxyl, the obtained H‐Mn₃O₄–PEI–PtNPs–Ru aggregates locally to form sheet‐like nanostructures ((H‐Mn₃O₄–PEI–PtNPs–Ru)_n–Eu³⁺), by which the luminous efficiency is further increased. Based on the nanosheets and two designed peptides, a sandwiched ECL biosensor, using palladium nanocages synthesized through galvanic replacement reaction as substrate, is proposed for CA2 with a linear range from 0.001 to 100 ng mL^?1 and a detection limit of 0.3 pg mL^?1.     

Enhancement of the photoelectrochemical response of poly(terthiophenes) by CdS(ZnS) core-shell nanoparticles

We have investigated the photoelectrochemical properties of hybrid films of polythiophenes poly(4,4″dimethoxy-3′-methyl-2,2′:5′,2″ terthiophene) (PDM), poly(4,4″dipentoxy-3′-methyl-2,2′:5′,2″ terthiophene) (PDP), and cadmium sulfide/zinc sulfide (CdS(ZnS)) core-shell nanoparticles. Although CdS(ZnS) nanoparticles present enhanced exciton trapping, light harvesting by hybrid films was enhanced when compared to those of pure PDM and PDP films. This enhancement is explained in terms of electron and hole transfer mechanisms at different excitation wavelengths. The more efficient light harvesting of PDM/CdS(ZnS) when compared to that of PDP/CdS(ZnS) was attributed to its broader absorption spectrum and more efficient electron hopping.     

Unique electrochemiluminescence behavior of Ru(bpy)3 in a gold/Nafion/Ru(bpy)3 composite

The unique electrochemiluminescence (ECL) behavior of tris(bipyridine) ruthenium(II) (Ru(bpy)₃²⁺) immobilized in a gold/Nafion/Ru(bpy)₃²⁺ composite material was investigated. In this composite, the Ru(bpy)₃²⁺ ECL was found mainly occurred at 0-0.4 V during the cathodic scan process and the ECL peak was at about 0.1 V, which was quite different to the reported Ru(bpy)₃²⁺ ECL. Similar to the generally observed Ru(bpy)₃²⁺ ECL, the present ECL also could be enhanced by tri-n-propylamine (TPA). It is also unique that in the presence of TPA, another ECL peak at about 0.38 V occurred. These two ECL peak potentials all could be used as characteristic potential for the ECL determination of TPA.     

Photosensitization of Nanocrystalline SnO2 Films with a tris(2,2′‐Bipyridine) Ruthenium(II)‐Fullerene Dyad

Abstract

A photoelectrochemical study of a tris(2,2′‐bipyridine)ruthenium(II)‐C₆₀ donor–acceptor dyad adsorbed on nanocrystalline semiconductor SnO₂ electrodes has been carried out. The results show that the incident photon‐to‐current conversion efficiency of dyad‐based photoelectrochemical cells is ～10%.     

Synthesis and magnetic properties of an iron 1,2-bisthienyl perfluorocyclopentene photochromic coordination compound

The coordination compound Fe(BM-4-PTP)₂(NCS)₂⋅2MeOH (1) including the photoisomerizable ligand BM-4-PTP (1,2-bis(2′-methyl-5′-(pyrid-4″-yl)thien-3′-yl)perfluorocyclopentene) was obtained as an orange powder. The powder turns blue upon photocyclization of the 1,2-bisthienyl photochromic ligand induced by UV light irradiation at room temperature. Photocycloreversion is obtained by visible light irradiation of the material in the solid state. The orange and blue powders were investigated over the temperature range (5-293 K) and pressure range (1 bar-12 kbar) by magnetic susceptibility measurements and variable temperature ⁵⁷Fe Mössbauer spectroscopy. The photo-induced colour change is accompanied by a distinct magnetic variation at room temperature. Potentialities of this functional optical material for display and data recording are introduced.     

High organosolubility and optical transparency of novel polyimides derived from 2′,7′-bis(4-amino-2-trifluoromethylphenoxy)-spiro (fluorene-9,9′-xanthene)

A novel spiro(fluorene-9,9′-xanthene) skeleton bis(ether amine) monomer, 2′,7′-bis(4-amino-2-trifluoromethylphenoxy)-spiro(fluorene-9,9′-xanthene), was prepared through a simple acid-catalyzed condensation reaction of 9-fluorenone with resorcinol to form the spiro framework through an sp³ carbon atom. Subsequent nucleophilic substitution reaction of spiro[fluorene-9,9′-(2′,7′-dihydroxyxanthene)] with 2-chloro-5-nitrobenzotrifluoride in the presence of potassium carbonate in N,N-dimethylacetamide, was followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of new polyimides were synthesized from the diamine with various commercially available aromatic tetracarboxylic dianhydrides via a conventional two-stage process with the thermal or chemical imidization of the poly(amic acid) precursors. Most of the polyimides obtained from both routes were soluble in many organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide and m-cresol. All the polyimides could afford transparent, flexible, and strong films with low moisture absorptions of 0.35–0.64% and low dielectric constants of 2.63–3.09 at 1 kHz. Thin films of these polyimides showed an UV–vis absorption cutoff wavelength at 356–384 nm, and those of polyimides from 4,4′-oxydiphthalic dianhydride and 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) were essentially colorless. The polyimides exhibited excellent thermal stability, with decomposition temperatures (at 10% weight loss) above 540 °C in both air and nitrogen atmospheres and glass transition temperatures (T_g) in the range of 274–323 °C.     

Photo/electroluminescence properties of an europium (III) complex doped in 4,4′-N,N′-dicarbazole-biphenyl matrix

The photoluminescence properties of one europium complex Eu(TFNB)₃Phen (TFNB = 4,4,4-trifluoro-1-(naphthyl)-1,3-butanedione, Phen = 1,10-phenanthroline) doped in a hole-transporting material CBP (4,4′-N,N′-dicarbazole-biphenyl) films were studied. A series of organic light-emitting devices (OLEDs) using Eu(TFNB)₃Phen as the emitter were fabricated with a multilayer structure of indium tin oxide, 250 Ω/square)/TPD (N,N′-diphenyl-N,N′-bis(3-methyllphenyl)-(1,1′-biphenyl)-4,4′-diamine, 50 nm)/Eu(TFNB)₃phen (x): CBP (4,4′-N,N′-dicarbazole-biphenyl, 45 nm)/BCP (2,9-dimethyl-4,7-diphenyl-l,10 phenanthroline, 20 nm)/AlQ (tris(8-hydroxy-quinoline) aluminium, 30 nm)/LiF (1 nm)/Al (100 nm), where x is the weight percentage of Eu(TFNB)₃phen doped in the CBP matrix (1-6%). A red emission at 612 nm with a half bandwidth of 3 nm, characteristic of Eu(III) ion, was observed with all devices. The device with a 3% dopant concentration shows the maximum luminance up to 1169 cd/m² (18 V) and the device with a 5% dopant concentration exhibits a current efficiency of 4.46 cd/A and power efficiency of 2.03 lm/W. The mechanism of the electroluminescence was also discussed.     

White organic light-emitting diodes from three emitter layers

Three-wavelength white organic light-emitting diodes (WOLEDs) were fabricated using two doped layers, which were obtained by separating the recombination zones into three emitter layers. A sky blue emission originated from the 4,4′-bis(2,2′-diphenylethen-1-yl)biphenyl (DPVBi) layer. A green emission originated from a tris(8-quinolinolato)aluminum (III) (Alq₃) host doped with a green fluorescent 10-(2-benzothiazolyl)-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-[1]benzopyrano [6,7,8-ij]-quinolizin-11-one (C545T) dye. An orange emission was obtained from the N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) host doped with a red fluorescent dye, 4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB). A white light resulted from the partial excitations of these three emitter layers by controlling the layer thickness and concentration of the fluorescent dyes in each emissive layer simultaneously. The electroluminescent spectrum of the device was not sensitive to the driving voltage of the device. The white light device showed a maximum luminance of approximately 53,000 cd/m². The external quantum and power efficiency at a luminance of approximately 100 cd/m² were 2.62% and 3.04 lm/W, respectively.     

High efficiency red organic light-emitting diodes using a phosphorescent iridium complex doped into a hole-blocking material

We demonstrate high-efficiency red electrophosphorescent organic light-emitting devices (OLEDs) by doping a red-emitting iridium complex, Bis[7-methyl-1-p- tolyisoquinolinato-N,C²′]-iridium(III)(acetylacetonate) [(7-mtiq)₂Ir(acac)], into a hole-blocking material, 4-biphenyloxolato aluminum(III)bis(2-methyl-8- quinolinato)4-phenylphenolate. Both the phosphorescent characteristics of (7-mtiq)₂Ir(acac) and the electroluminescence mechanisms of OLEDs are investigated in this study. The Commission Internationale de L'Eclairage coordinates of (0.66, 0.34) is very close to the National Television System Committee standard red point (0.66, 0.33). With a dopant concentration of about 4%, a maximum luminance of 31317 cd/m² and a luminous efficiency of 21.6 cd/A have been obtained.