Enhanced reverse saturable absorption and optical limiting in heavy-atom-substituted phthalocyanines

The reverse saturable absorption and the optical-limiting response of metal phthalocyanines can be enhanced by use of the heavy-atom effect. Phthalocyanines containing heavy-metal atoms, such as In, Sn, and Pb, show a nearly factor-of-2 enhancement in the ratio of effective excited-state to ground-state absorption cross sections compared with those containing lighter atoms, such as Al and Si. In an f/8 optical geometry, homogeneous solutions of heavy-metal phthalocyanines, at 30% linear transmission, limit 8-ns 532-nm laser pulses to ≤ 3 µJ the energy for 50% probability of eye damage) for incident energies as high as 800 µJ

The photochemistry and photophysics of a series of alpha octa(alkyl-substituted) silicon, zinc and palladium phthalocyanines

Photophysical and photochemical measurements have been made on a series of novel alpha octa(alkyl-substituted) silicon, zinc and palladium phthalocyanines for which the synthesis is outlined. Fluorescence quantum yields and lifetimes, triplet quantum yields and lifetimes and singlet delta oxygen quantum yields were measured in 1% v/v pyridine in toluene. The effects of varying central atom and addition of alkyl substituents relative to unsubstituted parent molecules, zinc phthalocyanine (ZnPc) and silicon phthalocyanine (SiPc), are discussed. All phthalocyanines studied exhibit absorption and emission maxima in the region of 680–750 nm with molar absorptivity of the Q-band 105 M−1 cm−1. The series of compounds also exhibited triplet quantum yields of 0.65–0.95 and singlet oxygen quantum yields of 0.49–0.93

The Voltammetric Study of the Reduction of Tetraalkylammonium Perchlorate by Fe(TPP)\u3csup\u3e2-\u3c/sup\u3e

Tetraalkylammonium ions react with Fe(TPP)2− to form Fe(TPP)(R)− and trialkylamine. The tetrabutylammonium cation was verified to be the source of the alkyl group in the product, Fe(TPP)(R)−, by using (1H5C2)3(2H5C2)N− as the cation and 2H NMR. The reaction of Fe(TPP)2− with Bu4N− was monitored by cyclic voltammetry and thin layer spectroelectrochemistry. The activation parameters were measured, and were most consistent with an electron transfer (ET) mechanism. The rate of the reaction of tetramethyl and tetraethylammonium ions with Fe(TPP)2− was also examined. The rate constant decreased significantly as the carbon chain length decreased, which was also consistent with an ET mechanism

Liquid crystalline properties of unsymmetrically substituted phthalocyanines: structural features leading to nematic mesophase materials

A novel homologous series of four 1,4,8,11,15,18-hexakis(pentyl)-22-methyl-25-hydroxyalkylphthalocyanine derivatives with the hydroxyalkyl chain varying from hydroxynonyl through to hydroxydodecyl has been synthesized to investigate the role of the hydroxyalkyl chain in promoting thermotropic liquid crystalline behavior. Polarizing optical miscoscopy reveals that the compound with the shortest hydroxyalkyl chain (hydroxynonyl) exhibits a mesophase with a texture characteristic of a columnar mesophase, common among liquid crystalline phthalocyanine derivatives. However, as the chain is lengthened along the series, there appears a second type of mesophase that shows a schlieren texture. Such a texture is characteristic of a nematic phase and rare among liquid crystalline phthalocyanine derivatives. A fifth compound, the novel 1,4,8,11,15,18-hexakis(pentyl)-22-methyl-25- dodecylphthalocyanine, exhibits only columnar mesophase behavior suggesting that the hydroxyl group at the end of the longer chains of the former compounds is important in developing the nematic phase

Electrochemical sensors modified with combinations of sulfur containing phthalocyanines and capped gold nanoparticles: A study of the influence of the nature of the interaction between sensing materials

Producción CientíficaVoltametric sensors formed by the combination of a sulfur-substituted zinc phthalocyanine (ZnPcRS) and gold nanoparticles capped with tetraoctylammonium bromide (AuNPtOcBr) have been developed. The influence of the nature of the interaction between both components in the response towards catechol has been evaluated. Electrodes modified with a mixture of nanoparticles and phthalocyanine (AuNPtOcBr/ZnPcRS) show an increase in the intensity of the peak associated with the reduction of catechol. Electrodes modified with a covalent adduct-both component are linked through a thioether bond-(AuNPtOcBr-S-ZnPcR), show an increase in the intensity of the oxidation peak. Voltammograms registered at increasing scan rates show that charge transfer coefficients are different in both types of electrodes confirming that the kinetics of the electrochemical reaction is influenced by the nature of the interaction between both electrocatalytic materials. The limits of detection attained are 0.9 × 10−6 mol∙L−1 for the electrode modified with the mixture AuNPtOcBr/ZnPcRS and 1.3 × 10−7 mol∙L−1 for the electrode modified with the covalent adduct AuNPtOcBr-S-ZnPcR. These results indicate that the establishment of covalent bonds between nanoparticles and phthalocyanines can be a good strategy to obtain sensors with enhanced performance, improving the charge transfer rate and the detection limits of voltammetric sensors.Ministerio de Economía, Industria y Competitividad - Fondo Europeo de Desarrollo Regional (projects RTI2018-097990-B-I00 / CTQ2017-87102-R)Junta de Castilla y Leon - Fondo Europeo de Desarrollo Regional (project VA275P18

Uranyl phthalocyanines show promise in the treatment of brain tumors

Processes synthesize sulfonated and nonsulfonated uranyl phthalocyanines for application in neutron therapy of brain tumors. Tests indicate that the compounds are advantageous over the previously used boron and lithium compounds