Synthesis and spectral properties of axially substituted zirconium(IV) and hafnium(IV) water soluble phthalocyanines in solutions

Methods of synthesis of novel water soluble axially substituted Zr(IV) and Hf(IV) phthalocyanines with gallic, 5-sulfosalicyllic, oxalic acids, and methyl ester of gallic acid as axial ligands coordinated to the central atom metal of phthalocyanine are presented. The absorption spectra of complex solutions in various solvents were characterized. The dependence of the spectral red shift from Reichardt’s empirical polarity parameter is described. The deviation from the linearity of Beer–Bouguer–Lambert law was investigated for the range of concentration 5×10⁻⁶ to 10×10⁻⁵ M. Fluorescent properties of axially substituted phthalocyaninato metal complexes in DMSO solutions were investigated.     

Synthesis,electrochemical and spectroelectrochemical properties of highly soluble tetra substituted phthalocyanines with [4-(thiophen-3-yl)-phenoxy]

Zinc, oxo-titanium, cobalt, and manganese phthalocyanine derivatives substituted with nonperipheral 3-(tetra[4-(thiophen-3-yl)-phenoxy] moieties have been synthesized and characterized by elemental analysis, IR, ¹H NMR spectroscopy, electronic spectroscopy, and mass spectra. The compounds have good solubility in various polar and nonpolar organic solvents and not aggregated (in the same solvents) within a wide concentration range. Electrochemical and spectroelectrochemical measurements exhibit that incorporation redox active metal centers, Co^II, Ti^IVO and Mn^IIIOAc into the phthalocyanine core extend the redox richness of the Pc ring with the reversible metal-based reduction and oxidation couples of the metal centers in addition to the common Pc ring-based electron transfer processes.     

Luminescent monomer of substituted tetrastyrylpyrene and poly(p-phenylenevinylene) derivative with pyrene segments: Synthesis and photophysics

1,3,6,8-Tetrabromopyrene reacted with 1-tert-butyl-4-vinylbenzene to afford the luminescent monomer M. In addition, the reaction of 1,6-dibromopyrene with 1,4-didodecyloxy-2,5-divinylbenzene yielded a poly(p-phenylenevinylene) (PPV) derivative P. M dissolved partially in chloroform and completely in THF. P showed an excellent solubility being readily soluble in common organic solvents. M emitted intense blue–green light in THF solution with photoluminescence (PL) maximum at 507 nm and green–yellow light in thin film with PL maximum at 570 nm. Polymer P displayed in THF a PL maximum at 464 nm and a shoulder at 513 nm. Thin film of this polymer exhibited PL maximum at 572 nm. Both M and P emitted from excimers in solid state. The PL emission quantum yields in THF were 0.35 for M and 0.32 for P. The emission maximum of M thin film was red shifted by 9 nm after annealing at 150 °C for 24 h as a result of conformational changes of the molecules with increase in temperature.     

Poly(p-phenylenevinylene) derivatives with conjugated thiophene side chains: Synthesis,photophysics and photovoltaics

Three novel poly(p-phenylenevinylene) (PPV) derivatives with conjugated thiophene side chains, P1, P2 and P3, were designed and synthesized for application in polymer solar cells (PSCs). The effects of the conjugated side chains on the thermal, photophysical, electrochemical and photovoltaic properties of these polymers were investigated. The polymers exhibited good thermal stability and film-forming ability. The absorption spectra indicated that the short conjugated side chains have slight influence on the UV-region spectra of PPVs; whereas with increasing the length of conjugated side chains, the absorption of the UV-region red-shifted. The photoluminescence spectra reveal that complete exciton energy transfer occur from the conjugated side chains to the main chains of the polymers. The polymers emitted yellow-orange light with the emission maximum peaks in the region of 525–550 nm in chloroform solution and 611–616 nm in thin films. Cyclic voltammograms displayed that the band gaps were reduced effectively by the attachment of the conjugated thiophene side chains. The bulk heterojunction solar cells were fabricated based on the blend of the polymers and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in a 1:4 weight ratio. The maximum power conversion efficiency (PCE = 0.53%) was obtained by using P3 as the electron donor under the illumination of AM 1.5, 100 mW/cm².     

Synthesis, structure and fluorescence properties of a highly stable indium(III)-2,5-pyridinedicarboxylate coordination polymer

The hydrothermal reaction of 2,5-pyridinedicarboxylic acid (H₂PDC), diethylene triamine and In(NO₃)₃·4.5H₂O gave rise to a two-dimensional (2D) coordination polymer In(OH)(2,5-PDC). This compound crystallizes in the orthorhombic space group Iba2, with cell parameters, a = 12.656(3) Å, b = 20.114(4) Å, c = 6.2216(1) Å, V = 1583.9(5) Å³ and Z = 8. Its structure contains one-dimensional In–O–In–O– chains, which are further linked by 2,5-PDC ligands into a 2D supramolecular neutral framework. The adjacent 2D layers are parallel with each other and construct a three-dimensional framework via hydrogen bands. At room temperature, the compound exhibits intense photoluminescence. On the basis of the results of TG/DTA analyses, the structure is thermally stable up to 390 °C.     

Copper(II) complexes containing tetrathiafulvalene substituted by a bipyridine ligand: Synthesis, X-ray diffraction and EPR characterizations

We report a preliminary study of two novel complexes combining a paramagnetic transition metal (Cu(II)) and a cyclophane-type TTF-bipyridine ligand TTF-bipy = (cis)2,7-bis(pentylsulfanyl)-3,6-[2,2′-bipyridine-bis(4,4′-methanediyl)bis-sulfanyl]tetrathiafulvalene. The syntheses of the complexes Cu(hfac)₂(TTF-bipy) (hfac = hexafluoroacetylacetonate) and Cu(NO₃)₂(TTF-bipy)·H₂O are reported. The results of single-crystal EPR measurements are discussed on the basis of structural features deduced from preliminary X-ray diffraction data and indicate that these neutral molecular complexes behave as isolated paramagnetic units.     

A series of water soluble RE(III) complexes: Synthesis,characterization, photophysical property and sensing activity towards Cr(III)

In this paper, four water soluble rare-earth(III) fluorescent chemosensors, Na₃RE(PDA)₃ (PDA = pyridine-2,6-dicarboxylic acid, and RE = Sm, Eu, Tb, Dy), are synthesized and characterized. Their excitation and emission spectra, fluorescence responses towards Cr(III), quenching mechanism, oxygen and thermal sensitivity of the complexes are systemically studied. The emission intensity and the excited state lifetimes of the four complexes decrease with increasing concentration of trivalent chromium (Cr(III)). Their sensing behavior towards Cr(III) is investigated by fluorescence spectroscopy. Results suggest that Na₃Dy(PDA)₃ exhibits highest sensitivity and linear spectral response towards Cr(III) (Stern–Volmer constant = 0.461 × 10⁷ L/mol, linearity = 0.996). It is note worthy that oxygen has little effect on the emission of Na₃RE(PDA)₃ complexes. These important advantages make themselves promising candidates to be utilized in actual applications.     

Synthesis,spectroscopy and electrochemistry study on a novel di-silyl substituted poly(p-phenylenevinylene)

A novel di-silyl substituted poly(p-phenylenevinylene) (PPV) derivative is synthesized through the Gilch route. The polymer is solution processable and shows high thermal stability in air. UV–Vis spectra for the film and solution samples illustrate some different features, in which the absorption peak corresponding to the π–π* transition of the delocalized electrons along the polymer back bone is red shifted and broadened in the film state compared to the solution one. The fluorescent emission spectra are quite similar for the polymer in solution and in the solid states. Cyclic voltammetric investigation reveals a partially reversible n-doping process and an irreversible p-doping process. The cathodic current is much greater than that of the anodic one, which means the polymer has the tendency to be charged through n-doping rather than p-doping process. The improved affinity of the polymer to electrons may be owing to the low interface barrier between the polymer films and the electrode surface. The HOMO and LUMO energy levels have also been estimated from the data of oxidation and reduction onset potentials. All of the results indicate that the synthesized polymer is a promising green emissive material for the light-emitting device application.     

Theoretical studies on structures and spectroscopic properties of highly efficient phosphorescent iridium(III) complexes with pyrazine and pyrimidine ligands

A series of iridium(III) complexes (C^N)₂Ir(acac) (C^N = mppz (1), fmppz (2), ppm (3), and fppm (4); acac = acetoylacetonate, mppz = 2-methyl-3-phenylpyrazine, fmppz = 2-(2,4-difluorophenyl)-3-methylpyrazine, ppm = 2-phenylpyrimidine, and fppm = 2-(2,4-difluorophenyl)-pyrimidine) have been investigated theoretically to explore their electronic structures and spectroscopic properties. The structures in the ground and excited states have been optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. The calculated bond lengths of Ir–N, Ir–C, and Ir–O in the ground state agree well with the corresponding experimental results. Upon excitation, the bond lengths of Ir–N and Ir–C lengthen by 0.03 Å and that of Ir–O shortens by 0.02 Å compared with those in the X¹A ground states. At the TD-DFT and PCM levels, 1–4 give rise to absorptions at 499, 457, 460, and 427 nm and phosphorescent emissions at 549, 519, 505, and 465 nm, respectively. The HOMOs of 1–4 are mainly localized on the metal atom and C^N ligands, while the LUMOs are the π*(C^N) type orbital. Therefore, the transitions of 1–4 are all attributed to {[d(Ir) + π(C^N)] → [π*(C^N)]} charge transfer. It is shown that the emissions are significantly dominated by the metal participating in the frontier molecular orbitals and affected by the C^N ligands but are hardly perturbed by the acac ligand.     

Morphology and fluorescence quenching in photovoltaic samples containing fullerene and poly(p-phenylene-vinylene) derivatives

We have studied the morphology of different heterogeneous samples containing poly[2-methoxy,5-(3′,7′-dimethyl-octyloxy)]-p-phenylene-vinylene (MDMO-PPV) and either fullerene (C₆₀) or 6,6-phenyl C₆₁-butyric acid methyl ester (PCBM) using atomic force microscopy in the shear force detection mode or pulsed-force mode and near-field scanning optical microscopy. These investigations confirm the large influence of preparation conditions on the morphology. Systematic variation of the layer thicknesses in two-layer samples indicate that fluoresecence quenching is restricted to an interface layer with a thickness of about 40 nm.     

Synthesis,spectroscopy and electroluminescence of cadmium(II) polypyridyl complexes

Five new complexes [Cd(ptpy-R)₂](PF₆)₂ (ptpy = 4′-phenyl-2,2′:6′,2″-terpyridine; R = tert-Butyl (1), hexyloxy (2), carbozole-9-yl (3), naphthalene-1-yl-phenylamine-N-yl (4) and diphenylamine-N-yl (5)) were synthesized and characterized by ¹H NMR, elemental analyses, UV–vis spectroscopy and cyclic voltammetry. The emission color of resultant complex molecules has been tuned effectively, from violet (397 nm) for 1 to orange (602 nm) for 5 in film, by modifying the electron-donating ability of the substituent R. The UV–vis spectroscopy and the solution-state luminescence showing remarkable solvatochromism suggests the emission involves the intra-ligand charge transfer (¹ILCT) excited state, occurring from the substituent R moiety to Cd(II) coordinated terpyridine. The electroluminescence (EL) properties for these organic materials were also studied and complexes 3, 4 and 5 exhibit EL wavelength at 548 nm, 596 nm and 604 nm with maximum current efficiency of 3.25 cd/A, 3.15 cd/A and 2.16 cd/A, respectively.     

Iridium(III) complexes with cyclometalated styrylbenzoimidazole ligands: Synthesis,electrochemistry and as highly efficient emitters for organic light-emitting diodes

Two phosphorescent iridium complexes (psbi)₂Ir(acac) and (ppbi)₂Ir(acac) (psbi = 1-phenyl-2-styryl-1H-benzo[d]imidazole, ppbi = 1-phenyl-2-(1-phenylprop-1-en-2-yl)-1H-benzo[d]imidazole, acac = acetylacetonate) were synthesized, and their photophysical, electrochemical and electroluminescent properties were also studied. Organic light-emitting devices with these two complexes as dopant emitters having the structure ITO/NPB (10 nm)/TCTA (20 nm)/x%Ir:CBP (y nm)/BCP (10 nm)/LiF (1 nm)/Al (100 nm) were fabricated. The device based on (psbi)₂Ir(acac) exhibited a maximum brightness of 56,162 cd m^?2, while the device based on (ppbi)₂Ir(acac) gave a maximum brightness of 31,232 cd m^?2. At high brightness of 1000 cd m^?2 and 10,000 cd m^?2, high current efficiencies of 25.7 cd A^?1 and 20.7 cd A^?1 were achieved, respectively, for the (psbi)₂Ir(acac)-based EL device. For the EL device based on (ppbi)₂Ir(acac), current efficiencies of 20.1 cd A^?1 at 1000 cd m^?2 and 14.2 cd A^?1 at 10,000 cd m^?2 were observed.     

Investigation on the syntheses and structures of Y~(Ⅲ) complexes with ami-nopolycarboxylic acids (Ⅳ)

This paper deals with the structure of the YIII complex with aminopolycarboxylic acids, synthesis and structural determination of the complex (NH4)[YIII(edta)(H2O)3]·3H2O (edta = ethylenediaminetetraacetic acid). The crystal and molecular structures of the (NH4)[YIII(edta)(H2O)3]·3H2O complex have been determined by single-crystal X-ray structure analysis. The crystal of the complex (NH4)[YIII(edta)(H2O)3]·3H2O belongs to orthorhombic crystal system and fdd2 space group. The crystal data are as follows: a=1.944 1(9) nm, b= 3.545 9(18) nm, c = 1.219 6(6) nm, V= 8.407 (7)nm3,Z=16, Mr= 503.25, Dc= 1.590g.cm3, μ= 2.844 mm 1 and F(000) = 4 160. The final R and Ru are 0.048 6 and 0.133 2 for 3 388 (I>2σ(I)) unique reflections, respectively. The complex anion [YIII(edta)(H2O)3] has a pseudo-mono-capped square antiprismatic nine-coordinate structure in which the six coordinate atoms (two N and four O) are from an edta ligand and three water molecules coordinate to the central YIII ion directly. From the res     

Synthesis and characterization of a new poly(aryl ether ketone) containing zinc phthalocyanine

A novel poly(aryl ether ketone) (PAEK) copolymer with metallophthalocyanine units was synthesized by the reaction of PAEK containing dicyanophenyl with excess amounts of 1,2-dicyanobenzene and zinc chloride in quinoline. This copolymer exhibits high glass transition temperatures and excellent thermal stability. This copolymer shows strong optical absorption in the visible region, and exhibits strong blue photoluminescence. Furthermore, this polymer can form differently aggregated structures in chloroform with the addition of 4,4′-bipyridine (Bipy). In particular, when polymer was mixed with 4 equiv. of Bipy, a uniform cotton like superstructure was observed. These results indicated that the axial coordination of zinc phthalocyanine and Bipy plays an important role in controlling the polymer morphologies obtained by the addition of Bipy to solutions of the polymer in CHCl₃.     

EPR studies of (Bi, Pb)-2223 phase substituted by Ruthenium ions

This work studied X-ray powder diffraction (XRD), electrical resistivity and electron paramagnetic resonance (EPR) measurements for Bi_1.8Pb_0.4Sr₂Ca_2.1Cu_3−xRu_xO_10+δ (0.0 ≤ x ≤ 0.4) superconducting samples. XRD analysis and electrical resistivity data showed that the low-content of Ru, x ≤ 0.05, enhanced both the phase formation and the superconducting transition temperature of (Bi, Pb)-2223 phase. A phase change from (Bi, Pb)-2223 phase to (Bi, Pb)-2212 phase was reported for x ≥ 0.15. Two EPR lines were observed for 0.0 ≤ x ≤ 0.075, indicating the presence of both (Bi, Pb)-2223 and (Bi, Pb)-2212 phases. While, one EPR line was observed for x ≥ 0.15, corresponding to the (Bi, Pb)-2212 phase formation. The number of spins (N) participating in the resonance and its spin paramagnetic susceptibility (χ), for the two phases, were calculated as a function of both Ru-content and temperature. In addition, we reported the variation of activation energy (E_a), Curie constant (C), Curie temperature (θ) and effective magnetic moment (μ) with Ru-content.     

Electrochemical synthesis,characterization and photophysics of a poly(fluorenylene vinylene) derivative

The electrosynthesis of a soluble poly(fluorenylene vinylene) derivative, namely poly(9,9-dioctyl-2,7-fluorenylene vinylene) (PDO27FV), its characterization, photophysical properties and electrochemistry are reported in this work. Photophysical studies indicate a strong dependence on the solvent employed, suggesting a highly polar excited state. The fluorescence quantum yield was estimated to be 0.52. Further, time-resolved photoluminescence exhibited two decays times, 0.68 and 1.31 ns, that are in agreement with a coupling deactivation process of the fluorenylene moiety, induced by the vinylene moiety. Electron affinity and ionization potential calculated from absorption and electrochemical data indicates that PDO27FV has potential to be applied as photoactive film in organic light emitting diodes and bulk heterojunction solar cells.     

Nano-structured Langmuir–Blodgett mixed films of titanyl(IV) phthalocyanine and bis(neopentylimido)perylene: Unique degree of miscibility

Langmuir and Langmuir–Blodgett (LB) films of mixed titanyl(IV) phthalocyanine (TiOPc)–bis (neopentylimido)perylene (BNPTCD) were fabricated and characterized. The surface pressure–area isotherms (π–A) of the mixed Langmuir films were recorded and revealed an unusual expansion of the surface area per molecule. The expansion is attributed to the interpenetration of the BNPTCD in the space available between adjacent Pc macrocycles preventing molecular stacking and forcing the expansion. This effect is a result of the high degree of mixing between species in the floating monolayer. This assumption was further supported by means of surface enhanced Raman scattering (SERS) mapping technique that proved the absence of large segregated domains in the LB film, in other words, the absence of phase separated regions, in agreement with a unique degree of miscibility.     

Analytical and electrical studies on poly(2-vinylpyridine) and its metal complexes

Poly (2-vinylpyridine) (P2VP) and its metal-based derivatives have been synthesized and characterized through analytical measurements such as melting point, molar mass and thermal analysis. The d.c. conductivity of these materials was studied as a function of temperature. The conductivity of P2VP is seen to increase by many orders of magnitude on complexation with the transition metals Cu, Co, Pt and Pd.     

Synthesis and high-temperature performance of Ti substituted α-Ni (OH) 2

Ti substituted α-Ni(OH)2 (c=2.121 nm, a =0. 307 nm) with perfect high-temperature performance was prepared by the co-precipitation method. The effects of Ti addition on the structure and the electrochemical properties were investigated. The results indicate that the substitution of Ti for Ni leads to the conversion of β-Ni(OH)2 to α-Ni(OH)2 and the increase of the inter layer distance along c-axis from 0. 464 nm to 0. 707 nm. Infrared study reveals that more anions(SO2-4 and CO2-3 ions) and H2O exist in the Ti substituted α-Ni(OH)2. The discharge capaciinhibition of the oxygen evolution at high temperature.     

N-正丁基异辛酰胺合成及其萃取Pt（IV）的性能

合成了N-正丁基异辛酰胺(BiOA),并对其从盐酸介质中萃取Pt(IV)进行了研究。结果表明:待萃液Pt(IV)浓度为1.000g·L-1,HCl浓度为5mol·L-1时,用2.0mol·L-1N-正丁基异辛酰胺-5%TBP-正辛烷按相比(O/A)1:1混合萃取Pt(IV),经过5min的萃取振荡,萃取率可达99.5%。此萃取体系中TBP对Pt(IV)无协萃效应;水是载Pt(IV)有机相的有效反萃剂,反萃率可以达到90.3%。N-正丁基异辛酰胺萃取Pt(IV)的反应是放热反应,反应热为–10.52kJ·mol-1。红外光谱分析表明,在1mol·L-1~5mol·L-1的HCl范围内,N-正丁基异辛酰胺萃取铂的反应为酸性离子缔合萃取。萃取反应为:PtCl62-+2BiOA(0)+2H+→[(BiOAH+)2·PtCl62-](0)。