Distorted Phthalocyanines by Click Chemistry: Photoacoustic,Photothermal, and Surface-Enhanced Resonance Raman Studies

Distortion of nominally planar phthalocyanine macrocycles affects the excited state dynamics in that most of the excited-state energy decays through internal conversion. A click-type annulation reaction on a perfluorophthalocyanine platform appending a seven-membered ring to the β-positions on one or more of the isoindoles distorts the macrocycle and modulates solubility. The distorted derivative enables photoacoustic imaging, photothermal effects, and strong surface-enhanced resonance Raman signals.     

Homogeneous catalysis by ruthenium carbonyl clusters

The historical background of and the incentive for using ruthenium carbonyl clusters as homogeneous catalysts are outlined. Keeping in view the possible solutions the uncertainties arising from declusterification and metal colloid formation are discussed. All ruthenium cluster-catalysed reactions are broadly classified as reactions with or without carbon monoxide as one of the reactants and the basic differences between such reactions are highlighted. Some of the factors of special relevance to cluster-catalysed reaction systems are mentioned. The reactions involving carbon monoxide are then discussed. These include water-gas-shift reaction, carbon monoxide hydrogenation, hydroformylation, reductive carbonylation of nitrobenzene and other carbonylation reactions. Hydrogenation, transfer hydrogenation, isomerisation and a few other reactions are then discussed. For all these reactions, special emphasis is laid on well-characterised cluster complexes that have been proposed as catalytic intermediates. Finally an attempt has been made to identify the path that future research in cluster catalysis is likely to follow.     

Monte Carlo simulation of phase separation and clustering in the ABV model

As a model for a binary alloy undergoing an unmixing phase transition, we consider a square lattice where each site can be either taken by an A atom, a B atom, or a vacancy (V), and there exists a repulsive interaction between AB nearest neighbor pairs. Starting from a random initial configuration, unmixing proceeds via random jumps of A atoms or B atoms to nearest neighbor vacant sites. In the absence of any interaction, these jumps occur at jump rates _A and _B, respectively. For a small concentration of vacancies (c _v=0.04) the dynamics of the structure factorS(k,t) and its first two momentsk ₁(t),k ₂ ² (t) is studied during the early stages of phase separation, for several choices of concentrationc _B of B atoms. Forc _B=0.18 also the time evolution of the cluster size distribution is studied. Apart from very early times, the mean cluster sizel(t) as well as the moments of the structure function depend on timet and the ratio of the jump rates (= _B/ _A) only via a scaled timet/(). Qualitatively, the behavior is very similar to the direct exchange model containing no vacancies. Consequences for phase separation of real alloys are briefly discussed.     

Evaluation of Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole as photostabilizer for poly(methyl methacrylate)

The photostabilization of poly(methyl methacrylate) (PMMA) films by Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole compounds was investigated. The PMMA films containing concentration of complexes 0.5% by weight were produced by the casting method from chloroform solvent. The photostabilization activities of these compounds were determined by monitoring the hydroxyl index with irradiation time. The changes in viscosity average molecular weight of PMMA with irradiation time were also tracked (using benzene as a solvent). The quantum yield of the chain scission (Φ_cs) of these complexes in PMMA films was evaluated and found to range between 4.19 × 10^?5 and 8.75 × 10^?5. Results obtained showed that the rate of photostabilization of PMMA in the presence of the additive followed the trend:[1] > [2] > [3] > [4] > [5].According to the experimental results obtained, several mechanisms were suggested depending on the structure of the additive. Among them, UV absorption, peroxide decomposer, and radical scavenger for photostabilizer mechanisms were suggested.     

Mechanism of phosphine photolysis. Application to Jovian atmospheric photochemistry

PH3 is photolyzed to H2 and P2H4 and the P2H4 in turn is converted to red phosphorus. The initial quantum yield of H2 formation was redetermined and found to be 0.93 +/- 0.07. Red phosphorus was identified by its chemical properties and the absence of P-H stretching bands in its infrared spectrum. The reaction pathway was not changed by lowering the PH3 partial pressure from 90 to 11 torr or by performing the photolysis in a 70-fold excess of H2. The initial quantum yields at 11 torr of PH3 are phi P2H4 = 0.04 +/- 0.02 and phi H2 = 0.74 +/- 0.08. The initial rate of P2H4 formation was not affected by lowering the PH3 temperature to 227 or 157 K. The yield was greater at 157 K because the P2H4 condensed and was protected from further destruction. The initial quantum yields for the formation of P2H4 and H2 in PH3-NH3 mixtures were comparable to those observed for PH3 alone. Photolysis of mixtures in which NH3 was absorbing 90% of the light resulted in the rapid formation of P2H4. No N2 was formed when PH3-NH3 mixtures were photolyzed, suggesting that the destruction of NH3 is quenched by PH3. The application of these findings to Jovian atmospheric chemistry is discussed.     

The effect of a substitutional Fe impurity on the magnetic properties of the antiferromagnetic FeRh alloy

We present a simple model for the band structure of the Fe_0.50Rh_0.50 anti-ferromagnetic alloy, and we study the effect of a substitutional Fe impurity on the magnetic properties of this alloy.     

Synthesis of new 14- and 16-membered macrocycles and their transition metal complexes

Summary Benzoylacetic acid (1 mol) interacts with ethylenediamine or with propanediamine (2 mol) to yield new N₄ macrocycles 1,5,8,12-tetraazacyclotetradeca-2,4,9,11-tetraphenyl-3, 10-dicarboxylic-4,11-diacetic acid- 1,8-diene (L¹) and 1,5,9,13-tetraazacyclohexadeca-2,4,10,12-tetraphenyl-3, 11-dicarboxylic-4,12-diacetic acid-1,9-diene (L²), respectively. These macrocycles have been successfully complexed with Cr^III, Fe^III, Mn^II, Co^II, Ni^II, Cu^II and Zn^II. The complexes of the divalent metal ions are non-electrolytes, while those of Fe^III and Cr^III are 1:1 electrolytes in DMSO. On the basis of ligand field spectra and magnetic moments an octahedral geometry has been proposed for all the complexes.     

Synthesis and characterization of new 13 and 14-membered macrocycles and their transition metal complexes

Two new macrocyclic ligands 1,4,7,9,12-pentaaza-10,11-dioxo-8,9,12,13-bis-(1-oxo-3-thio-2-hydropyrimidine)-trideca-7,13-diene, (L¹) and 1,4,7,9,12-pentaaza-10,12-dioxo-8,9,13,14-bis-(1-oxo-3-thio-2-hydropyrimidine)-tetradeca-7,14-diene, (L²) and their complexes with Cr^III, Mn^II, Fe^III, Co^II, Ni^II, Cu^II and Zn^II have been synthesized, and characterized by elemental analysis, i.r., ¹H-n.m.r., e.p.r., u.v.–vis. spectroscopy, magnetic susceptibility and conductance measurements. The conductivity measurements suggest that the complexes of divalent metal ions are 1:1 electrolytes whereas the trivalent metal ions are non-electrolytes. On the basis of electronic spectra and magnetic moment measurements the Cr^III and Fe^III complexes are octahedral, while the divalent metal complexes are tetrahedral except for the Ni^II and Cu^II complexes which are proposed to have square planar geometry. All the ligands and their complexes have been screened against gram-positive bacteria Staphylococcus aureus and gram-negative bacteria E. coli. The results show that they inhibit the growth of bacteria.     

An MCl inf4 p2− moiety (M = copper,zinc, cadmium and mercury) stabilized by bis(ethylenediamine)copper(II) cation

Summary New ionic bimetallic complexes of the type [Cu(en)₂]-[MCl₄], where M = Cu^II, Zn^II, Cd^II and Hg^II, were prepared by reacting bis(ethylenediamine)copper(II) dichloride (1 mol) with copper, zinc, cadmium and mercury dichlorides (1 mol) in absolute alcohol. Elemental analyses, conductivity and magnetic susceptibility measurements, and spectroscopic data (such as i.r., u.v.-vis. and e.p.r.) confirm that the compounds are 22 electrolytes in MeOH and that the copper(II) ion is paramagnetic, maintaining its square-planar geometry, while metal ions in the anionic moiety of the complexes achieve their usual tetrahedral environment. An augmented magnetic moment has been observed in the [Cu(en)₂] [CuCl₄] complex, which is attributed to the ferromagnetic effect and TIP.Author to whom all correspondence should be directed.     

Thermal studies on arsenic,antimony and bismuth alkylxanthate complexes

Six xanthate derivatives of arsenic(III), antimony(III), and bismuth(III) {(ROCS₂)₃M; R=methyl, ethyl, isopropyl, n-butyl, cyclohexyl and benzyl} have been prepared and the thermal behaviour investigated by thermogravimetry. A thermal decomposition mechanism for the complexes is proposed on the basis of the thermogravimetric data and mass spectral measurements.