Anionic water-soluble sulfonated phthalocyanines: microwave-assisted synthesis,aggregation behaviours,electrochemical and in-situ spectroelectrochemical characterisation

In this work, a phthalonitrile derivative bearing p-sulfonylphenoxy group at the 3-position has been synthesised. The water-soluble non-peripherally tetrasubstituted zinc (3) and cobalt (4) phthalocyanines were obtained by cyclotetramerisation of this phthalonitrile derivative in the presence of anhydrous metal salts by microwave irradiation. The compounds have been characterised by using FT-IR, ¹H NMR, UV–Vis and Mass spectrometry (MS) data. The aggregation behaviours of these compounds were investigated in methanol, DMSO, DMF, and water. We have also studied the aggregation behaviours of the phthalocyanine complex 3 in various DMSO/water mixtures. Additionally, the redox properties of the phthalocyanine complexes were examined in dimethylsulfoxide by voltammetry and in situ spectroelectrochemistry. Redox behaviours of the complexes supported the structures of the complexes. Metal and ring-based reductions were observed for 4 and only ring-based electron transfer processes were observed with 3.     

Synthesis and photophysicochemical properties of novel mononuclear rhodium(III) phthalocyanines

Chloro axially-substituted octa(4-isopropylphenoxy)rhodium(III)phthalocyanine, (R)₈PcRhCl (3), was reacted with the nitrogenous bases pyridine (Py) and pyrazine (Pyz) to give the axially-disubstituted octa(4-isopropylphenoxy)rhodium(III)phthalocyanines [(R)₈PcRhCl(L)] (4) and (5), L = (Py) and (Pyz), respectively. In this study, the fluorescence quantum yield (Φ_F), the phosphorescence quantum yield (Φ_phos) and the photodegradation quantum yield (Φ_pd) values for the newly synthesized rhodium phthalocyanine complexes (RhPcs) 4 and 5 are reported. The complexes have also been fully characterized by elemental analysis, FD mass spectrometry, FT-IR and ¹H NMR spectroscopy.     

Novel peripherally substituted zinc phthalocyanine: synthesis,characterization, investigation of photophysicochemical properties and theoretical study

The new thiohexanoic acid substituted zinc phthalocyanine was synthesized and characterized by FT-IR, ¹H–NMR, electronic spectroscopy, and mass spectrometry as well as DFT calculation studies. The photochemical properties (singlet-oxygen quantum yields and photodegradation quantum yields) and photophysical properties (fluorescence quantum yields and fluorescence behavior) of the compound were studied in dimethylsulfoxide (DMSO), dimethylformamide (DMF) and tetrahydrofuran (THF). Singlet-oxygen quantum yields ranged from 0.29 to 0.43. However, energy-minimized structure, vibrational frequency, electronic distribution and molecular orbitals were obtained by DFT calculations which were supported by experimental results.     

Synthesis and nonlinear optical properties of a novel indium phthalocyanine highly branched polymer

Due to the well‐known optical limiting properties of indium (III) phthalocyanines (In [III] Pcs) and aiming at extending their conjugation system, a highly branched indium phthalocyanine polymer was prepared. Flash chromatography was used for obtaining a pure polymer of polydispersity index near to the unity. The structure of the prepared polymer was determined using different spectroscopic techniques. Optical limiting and open aperture Z‐scan measurements were carried out according standard procedures. Compared with many other phthalocyanines, the prepared indium‐phthalocyanine polymer shows a high optical limiting performance that is indicated by a relatively low limiting threshold of 430 mJ cm^?2 and a large nonlinear absorption coefficient (α₂ = 3.4 × 10^?8 cmW^?1). Copyright © 2015 John Wiley & Sons, Ltd.     

Simultaneous determination of gallium(III) and indium(III) by derivative spectrophotometry

A simple, selective and sensitive derivative spectrophotometric method is proposed for the simultaneous determination of gallium(III) and indium(III) in mixtures using 1-(2-pyridylazo)-2-naphthol in cationic micellar medium, without any prior separation. Beer's law is obeyed between 2.80x10(-1)-3.63 and 4.60x10(-1)-9.20 mug ml(-1) concentration of Ga(III) and In(III) at 550 and 542 nm, the isodifferential points of indium and gallium complexes in the first-order derivative mode, respectively. The proposed method is successfully applied for the determination of gallium and indium in standard reference materials and synthetic binary mixtures with a relative error of +/-2.07 and +/-2.55%, respectively.     

The development of highly selective approaches to sandwich-type heteroleptic double- and triple-decker lutetium(III) and europium(III) phthalocyanine complexes

The selective synthesis of heteroleptic (heteronuclear) sandwich-type lanthanide phthalocyanines has been accomplished. Double-decker complexes ^BuPcLnPc, and ^BuPcLnPc^Cl (Ln = Lu, Eu; ^BuPc = 2,3,9,10,16,17,23,24-octabutylphthalocyaninate; Pc = phthalocyaninate, ^ClPc = 2,3,9,10,16,17,23,24-octachlorophthalocyaninate) were obtained in good yields by a direct interaction of metal-free ligand ^BuPcH₂ with the monophthalocyanines PcLnOAc or ^ClPcLnOAc. Heteronuclear triple-decker phthalocyanines PcEu^RPcLu^RPc, ^ClPcEu^RPcLu^RPc and ^BuPcEu^RPcLu^RPc (^RPc = ^BuPc, ^tBuPc; ^tBuPc = 2(3),9(10),16(17),23(24)-tetra-tert-butylphthalocyaninate) were obtained from the corresponding mono-(PcEuOAc, ^ClPcEuOAc, ^BuPcEuOAc) and bisphthalocyanines (^RPc₂Lu) under similar conditions.     

Aluminum(III), gallium(III), and indium(III) 4-hydroxyacridinato complexes

4-Hydroxyacridine (HAcr) is an O,N-chelating ligand whose coordination chemistry toward group 13 M(III) ions has received little attention. The molecular structure of HAcr consists of a 2,3-disubstituted-8-hydroxyquinoline; thus, in order to compare 8-hydroxyquinoline (HQ), 2-methyl-8-hydroxyquinoline (HMeQ′), and 2,3-disubstituted-8-hydroxyquinoline (HAcr) for steric and/or electronic influence, HAcr chelating ability toward the Al(III), Ga(III), and In(III) triad has been investigated. Irrespective of the nature of M(III), only complexes containing two equivalents of deprotonated HAcr are obtained. This article describes the synthesis and characterization of different series of bis-chelated pentacoordinated (Acr)₂MY (M = Al, Ga, In; Y = Cl, Br, I, NCS, N₃) or (Acr)₂MZ (M = Ga or In; HZ = C₆H₅OH, C₆H₁₃OC₆H₄OH, C₆H₅COOH, or C₆H₁₃OC₆H₄COOH) six-coordinate neutral (Acr)₂In(acac) (H(acac) =acetylacetone), or ionic [(Acr)₂In(N,N)][CF₃SO₃] (N,N = 2,2′-bipyridine or 1,10-phenanthroline) complexes. These results significantly contribute to elucidating the complexation capability of HAcr.     

Synthesis, photophysical and photochemical properties of aryloxy tetra-substituted gallium and indium phthalocyanine derivatives

The synthesis, photophysical and photochemical properties of the tetra-substituted aryloxy gallium(III) and indium(III) phthalocyanines are reported for the first time. General trends are described for photodegradation, singlet oxygen, fluorescence, and triplet quantum yields and triplet lifetimes of these compounds. The introduction of phenoxy and tert-butylphenoxy substituents on the ring resulted in lowering of fluorescence quantum yields and lifetimes, and triplet quantum yields, and an increase of k_IC, k_ISC, and k_F. Photoreduction of the complexes was observed during laser flash photolysis. The singlet oxygen quantum yields (Φ_Δ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.41 to 0.91. Thus, these complexes show potential as Type II photosensitizers.     

新型咪唑嵌合氨基亲水作用色谱固定相的制备及其色谱性能

发展新型高效的亲水作用色谱分离材料对于极性化合物的分离分析具有重要的意义。本文设计合成了一种新型咪唑嵌合的氨基亲水作用色谱固定相（Sil-IEASP）,并分别采用傅里叶变换红外光谱仪、热重分析仪和元素分析仪对该固定相进行了表征,结果表明该固定相制备成功。以核苷和核酸碱基为样品,分别考察了流动相中的水含量、盐浓度和pH对其保留的影响,结果表明所发展的固定相具有良好的亲水作用特性;此外,缓冲盐浓度和pH几乎不影响上述物质的保留。进一步将该固定相应用于分离尿嘧啶、腺嘌呤、胞嘧啶、尿苷和3种位置异构体（邻三联苯、间三联苯和苯并菲）,与常用的氨基固定相相比,本文所发展的固定相具有更好的分离效果,有望在亲水作用色谱分离领域发挥潜在的应用价值。     

Solvent extraction and separation of gallium(III), indium(III), and thallium(III) with tributylphosphate

A systematic study has been made of the solvent extraction behaviour of milligram amounts of gallium(III), indium(III), and thallium(III) with TBP from hydrochloric acid, and of thallium(III) from nitric acid, sulphuric acid and buffer solutions of different pH. The effect of the metal ion concentration, acid concentration, reagent concentration, salting-out agent, and diverse ions have been critically examined. A scheme for separation of gallium(III), indium(III), and thallium(III) from each other and for their determination is proposed.     

Kinetics and equilibria of the interactions of hydroxamic acids with gallium(III) and indium(III)

The thermodynamics and kinetics of the binding of Ga(III) and In(III) to two hydroxamic acids, C6H5-C(O)N(OH)H (BHA) and C6H5-C(O)N(OH)C6H5 (PBHA), have been investigated in acidic media. Spectrophotometric titrations in the UV region reveal that, with excess metal, only the chelate ML forms, whereas the concentration of the protonated species, MHL, is negligible. The thermodynamic parameters indicate that the driving force for formation of ML from MOH2+ and HL is mainly enthalpic, with entropic contributions favoring InL2+ and disfavoring GaL2+ formation. The kinetic (stopped-flow) experiments are interpreted on the basis of two parallel reaction paths both involving reaction of the undissociated ligand (HL): (a) M + HL <==> MHL <==> ML + H where MHL is in a steady state and (b) MOH + HL <==> ML + H2O. Whereas gallium binding to BHA and PBHA proceeds mainly through path b, indium binding to PBHA proceeds through both a and b paths. The rates of both the a and b steps are ligand dependent. Two alternative mechanisms are proposed. The first is based on the electronic characteristics of the ligands and is of the Ia type. The second, of the Id type, assumes that a considerable fraction of the ligand is unreactive owing to intramolecular hydrogen bonding (possibly including a water molecule) which blocks the reaction site. The reasons for preferring the former mechanism are discussed.     

Porphyrin-appended europium(III) bis(phthalocyaninato) complexes: synthesis, characterization, and photophysical properties

Mixed cyclization of 3-mono-, 4-mono-, or 4,5-di(porphyrinated) phthalonitrile compounds 2, 3, or 6 and unsubstituted phthalonitrile with the half-sandwich complex [EuIII(acac)(Pc)] (Pc=phthalocyaninate, acac=acetylacetonate) as the template in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in n-pentanol afforded novel porphyrin-appended europium(III) bis(phthalocyaninato) complexes 7-9 in 30-40% yield. These mixed tetrapyrrole triads and tetrad were spectroscopically and electrochemically characterized and their photophysical properties were also investigated with steady-state and transient spectroscopic methods. It has been found that the fluorescence of the porphyrin moiety is quenched effectively by the double-decker unit through an intramolecular photoinduced electron-transfer process, which takes place in several hundred femtoseconds, while the recombination of the charge-separated state occurs in several picoseconds. By using different phthalocyanines containing different numbers of porphyrin substituents at the peripheral or nonperipheral position(s) of the ligand, while the other unsubstituted phthalocyanine remains unchanged in these double-deckers, the effects of the number and the position of the porphyrin substituents on these photophysical processes were also examined.     

Reduced viscosity, rheology and morphological properties of sulfonated poly (ether ether ketone): Polyetherimide blends

Blends of poly (ether ether ketone) (SPEEK) and polyetherimide (PEI) were prepared in five different weight ratios, using N,N-dimethylacetamide (DMAc) as solvent. Reduced viscosity and rheological parameters of these blends were investigated. Cannon–Fenske viscometer was used to study the viscoelastic parameters of the salt-free polyelectrolyte blends and the data obtained was fitted in Fuoss–Strauss equation. Effects of temperature and concentration have been investigated. It was observed that the storage modulus (G′) and dynamic viscosity (η′) of the blends varies significantly as compare to pure SPEEK and PEI. Surface morphology and thermal behavior of the membranes were studied using scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). Form SEM results it was observed that the phase separation occurs at 25% PEI contents in blends.     

Double hydrophilic block copolymers of sodium(2‐sulfamate‐3‐carboxylate)isoprene and ethylene oxide

Poly(sodium(2‐sulfamate‐3‐carboxylate)isoprene)‐b‐poly(ethylene oxide) and poly(ethylene oxide)‐b‐poly(sodium(2‐sulfamate‐1‐carboxylate)isoprene)‐b‐poly(ethylene oxide) double hydrophilic block copolymers were prepared by selective post polymerization reaction of the polyisoprene block, of poly(isoprene‐b‐ethylene oxide) diblocks or poly(ethylene oxide‐b‐isoprene‐b‐ethylene oxide) triblock precursors, with N‐chlorosulfonyl isocyanate. The precursors were synthesized by anionic polymerization high vacuum techniques and had narrow molecular weight distributions and predictable molecular weights and compositions. The resulting double hydrophilic block copolymers were characterized by FTIR and potentiometric titrations in terms of the incorporated functional groups. Their properties in aqueous solutions were studied by viscometry and dynamic light scattering. The latter techniques revealed a complex dilute solution behavior of the novel block copolymers, resulting from the polyelectrolyte character of the functionalized PI block and showing a dependence on solution ionic strength and pH. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 606–613, 2006     

EPR investigation of the origin of the magnetic field effect on the dimerization of aluminum(III) and gallium(III) phthalocyanine chlorides in film structures

The origin of the magnetic field effect on the dimerization of aluminum(III) and gallium(III) phthalocyanine chloride films is revealed. The EPR technique is employed to demonstrate that the dimerization of the above coordination compounds occurs via a free radical pathway with the formation of phthalocyanine and OH radicals, thus resulting in the appearance of the magnetic moment in the studied compounds.     

Electrochemical and spectroelectrochemical properties of tetra-tert-butylphthalocyanine indium(III)

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Separation and preconcentration of gallium(III), indium(III), and thallium(III) using new hydrazone-modified resin.

Ga(III), In(III) and Tl(III) ions in the presence of different sulfate salts have been successfully separated using 1-(3,4-dihydroxybenzaldehyde)-2-acetylpyridiniumchloride hydrazone (DAPCH) loaded on Duolite C20 in batch and column modes. The obtained modified resin as well as the metal complexes was characterized by elemental analysis and infrared spectra. The extraction isotherms were determined at different pH values. Ga(III) and In(III) are sorbed from aqueous solution at pH 2.5 - 3.0 while Tl(III) is sorbed at 2.0. The stripping of the adsorbed ions can be carried out using different concentrations of HCl as eluent. The saturation sorption capacities of Ga(III), In(III) and Tl(III) were 0.82, 0.96 and 0.44 mmol g(-1), where the preconcentration factors are 150, 150 and 100, respectively. The metal(III):Duolite C20-DAPCH ratio was 1:2 for Tl(III) and 1:1 for In(III) and Ga(III). The loaded resin can be regenerated for at least 50 cycles. The utility of the modified resin was tested in aqueous samples and the results show an RSD value of < 5% reflecting their accuracy and reproducibility.     

Heterogeneous ion-exchange membranes based on sulfonated poly(1,4-phenylene sulfide) and linear polyethylene: preparation, oxidation stability, methanol permeability and electrochemical properties

Poly(1,4-phenylene sulfide) was sulfonated with chlorosulfonic acid in 1,2-dichloroethane. The product (IEC = 2.38 mequiv./g) was ground and sieved (mesh size 63 μm) to obtain small particles. The particles and linear polyethylene were mixed in various ratios and the resulting blends were press-molded at 150 °C to obtain the membranes. Membranes containing up to 66 wt.% of sulfonated particles could be prepared without any problem in mechanical strength. The membranes were characterized by their stability in oxidative environment, ionic conductivity, and diffusive permeability to methanol. The membrane containing 66 wt.% of sulfonated particles was almost as conductive as Nafion 117; it exhibited, however, much lower diffusive permeability to methanol. In a strongly oxidative environment (3% aqueous H₂O₂ at 70 °C), the prepared membranes were less stable than Nafion 117, but much more stable than membranes with sulfonated poly(styrene-co-divinylbenzene) particles. In preliminary laboratory tests with H₂/O₂ and direct methanol fuel cells, the prepared membranes with high concentrations of sulfonated particles performed similarly to Nafion 117.