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

Synthesis of chalcone-containing zinc and cobalt metallophthalocyanines; investigation of their photochemical, DPPH radical scavenging and metal chelating characters

In this study, two new phthalocyanines (M = Zn and Co) were synthesized using the (E)-4-(4-(3-(4- (benzyloxy)phenyl)acryloyl)phenoxy)phthalonitrile (3) as ligand prepared from the chemical reaction of 4- nitrophthalonitrile with (E)-3-(4-(benzyloxy)phenyl)-1-(4-hydroxyphenyl)prop-2-en-1-one (2). All compounds were characterized using by 1H-NMR, 13C-NMR, UV–Vis, FT-IR, and MALDI-TOF mass spectra. Singlet oxygen quantum yields of the synthesized compounds, aggregates in different solutions, metal chelating and 2,2- Diphenyl-1-picrylhydrazyl (DPPH) radical scavenging properties were reported

Water-soluble phthalocyanines containing azo dye; microwave-assisted synthesis and photochemical properties of ZnPcs

Novel water-soluble metallophthalocyanines (M: Co, Ni, Cu, Zn) containing azo dye were characterized. The structures were confirmed by IR, UV/vis, 1 H NMR, 13C NMR, mass spectroscopy, and elemental analysis. Photochemical properties and aggregation behavior of zinc phthalocyanines were investigated. Singlet oxygen quantum yields of the zinc phthalocyanines (2d, 3d, 5d, and 6d) were 0.8, 0.57, 0.71, and 0.46, respectively

Substituted Co(II) and Cu(II) metallophthalocyanines from new Schif base containing pyrrole units: Synthesis, characterization and investigation of photocatalytic activity on 2,3‑dichlorophenol oxidation

In this article, novel Schif base compound 1 bearing pyrrole moiety has been synthesized from the reaction of 1-hydroxybenzaldehyde with 1,2-aminophenylpyrrole for the frst time. The cobalt phthalocyanine and copper phthalocyanine (3–4) were prepared by the cyclotetramerization of the novel phthalonitrile compound 2 and the corresponding metal salts. The new phthalonitrile compound 2 was synthesized by the reaction between 4-((E)-{[2-(1H-pyrro-1-yl)phenyl]imino}methyl) phenol 1 and 4-nitrophthalonitrile in DMF. The all new compounds (1–4) have been characterized by FT-IR spectroscopy, 1 H-NMR/13C-NMR, mass, UV–Vis spectroscopy techniques and elemental analysis (for metallophthalocyanines). Chlorinebearing phenols are of a class of pollutants. They have been regarded as a potential risk to environment and human health. It is important to advanced efective techniques to remove chlorinated phenols in wastewater. For this purpose, we investigated that diferent parameters infuenced the photooxidation process were determined and 2,3-dichlorophenol oxidize to the less harmfull products with high conversion and yield in the presence of Cu(II) and Co(II) phthalocyanine catalysts

Особливості отримання і властивостей тонких плівок органічних напівпровідників

In recent decades, thin films of organic semiconductors (OS), or, as they are also called, organic molecular crystals, have attracted special attention in connection with a number of proposals for their use in functional units of modern electronics, and therefore in modern technological equipment. At the same time, the optical, electrophysical and photoelectric properties of OS are very important, which are determined both by the structure of organic molecules, that is, the starting material, and by the crystal structure of condensates, that is, by the technological conditions of film production. In this regard, this article presents the results of studies of some properties of OS and the technology of obtaining thin films based on them. OS are characterized by weak intermolecular bonds of the Van der Baals type, which causes the low energy of their crystal lattice. In this regard, the electronic structure of individual molecules during the formation of a crystal does not change significantly, and the properties of the crystals almost completely preserve the individual features of the molecules in combination with new properties caused by their collective interaction. This determines the main features of optical and electrophysical properties of OS, their energy structure of neutral and ionized states. In this article, it is experimentally confirmed that the planar structure of atoms of molecular crystals, in particular, linear acenes, and therefore the number of π-electrons responsible for exciton absorption in the visible region of the spectrum determines the position of the edge of their own optical absorption. It was also confirmed that the long-wavelength shift of the optical absorption edge of thin films of phthalocyanines is observed when atoms of heavy elements, for example, lead, are introduced into the molecule. When atoms of lighter elements are introduced into the phthalocyanine molecule, their planarity is not disturbed, and the long-wavelength shift of the edge is much smaller. An explanation of such changes is presented based on the interaction of foreign atoms with the π-electron system of phthalocyanine rings of neighboring molecules. The significant influence of the technological parameters of production, in particular the temperature of the substrate during thermal sputtering, on the crystal structure and optical properties of thin films of linear polyacenes and metallophthalocyanines has been demonstrated and substantiated. The possibility of controlling and presetting the necessary properties of thin-film condensates of molecular crystals is shown.В останні десятиліття привернули до себе особливу увагу тонкі плівки органічних напівпровідників (ОН), або, як їх ще називають, органічних молекулярних кристалів у зв’язку із цілим рядом пропозицій щодо їх використання у функціональних вузлах сучасної електроніки, а отже в сучасному технологічному обладнанні. При цьому дуже важливими є оптичні, електрофізичні та фотоелектричні властивості ОН, які визначаються як будовою органічних молекул, тобто вихідним матеріалом, так і кристалічною структурою конденсатів, тобто технологічними умовами отримання плівок. У зв’язку із цим, в даній статті викладені результати досліджень деяких властивостей OH і технології отримання тонких плівок на їхній основі. OH характеризуються слабкими міжмолекулярними зв’язками типу Ван-дер-Bаальсівських, що зумовлює низьку енергію їх кристалічної ґратки. У зв’язку із цим електронна структура окремих молекул при утворенні кристалу суттєво не змінюється, і у властивостях кристалів майже повністю зберігаються індивідуальні особливості молекул у поєднанні з новими властивостями, зумовленими їх колективною взаємодією. Це визначає головні особливості оптичних і електрофізичних властивостей ОН, їхню енергетичну структуру нейтральних та іонізованих станів. В даній статті експериментально підтверджено, що планарна структура атомів молекулярних кристалів, зокрема, лінійних аценів, а отже і  кількість π-електронів, які відповідають за екситонне поглинання у видимій області спектру визначає положення краю їх власного оптичного поглинання. Підтверджено також, що довгохвильовий зсув краю оптичного поглинання тонких плівок фталоціанінів спостерігається при введенні в молекулу атомів важких елементів, наприклад, свинцю. При введенні в молекулу фталоціаніну атомів легших елементів їхня планарність не порушується, і довгохвильовий зсув краю значно менший. Представлено пояснення таких змін на основі взаємодії чужорідних атомів з π-електронною системою фталоціанінових кілець сусідніх молекул. Продемонстровано і обґрунтовано суттєвий вплив технологічних параметрів отримання, зокрема, температури підкладки при термічному напиленні на кристалічну структуру і оптичні властивості тонких плівок лінійних поліаценів та металофталоціанінів. Показано можливість керувати і наперед задавати необхідні властивості тонкоплівкових конденсатів молекулярних кристалів

Synthesis and characterization of new-type soluble β-substituted zinc phthalocyanine derivative of clofoctol

In this work, we have described the synthesis and characterization of novel zinc (II) phthalocyanine bearing four 2-(2,4-dichloro-benzyl)-4-(1,1,3,3-tetramethyl-butyl)-phenoxy substituents on the peripheral positions. The compound was characterized by elemental analysis and different spectroscopic techniques, such as FT-IR, 1H NMR, MALDI-TOF, and UV-Vis. The Zn (II) phthalocyanine shows excellent solubility in organic solvents such as dichloromethane (DCM), n-hexane, chloroform, tetrahydrofuran (THF), and toluene. Photochemical and electrochemical characterizations of the complex were performed by UV-Vis, fluorescence spectroscopy, and cyclic voltammetry. Its good solubility allows a direct deposition of this compound as film, which has been tested as a solid-state sensing material in gravimetric chemical sensors for gas detection, and the obtained results indicate its potential for qualitative discrimination and quantitative assessment of various volatile organic compounds, among them methanol, n-hexane, triethylamine (TEA), toluene and DCM, in a wide concentration range

Applications of Vanadium Phthalocyanine in Catalytic, Acid-Based Medium to Couple Sugar Molecules

The vanadium-substituted tetraazatetrabenzoporphyrin, vanadium phthalocyanine, was synthesized via reflux and characterized using FITR and XRD analysis. Subsequent to synthesis, the vanadium phthalocyanine was studied as a catalyst in redox reactions to convert fructose to different molecules, the products were predominately levulinic methyl ester and heptadionic acid. The ability to convert fructose to other compounds, such as alkyl levulinic derivative, is an important process to help eliminate reliance on traditional chemical feed stocks and promote alternative fuels. Levulinic acid has been commonly used as a starting material in the synthesis of biofuels and a precursor for pharmaceuticals, plasticizers, THF derivatives, γ-valerolatone. In the present study reactions were performed under acidic conditions using strong acids, which included nitric, sulfuric, hydrochloric, and hydrobromic acids, open atmospheric reflux in methanol and the reaction products were analyzed using GC-MS. Levulinic methyl ester and heptadionic acid were identified along with other coupled carbon-carbon products resulting from the de-cyclization of the sugar and subsequent coupling in a single pot reflux. The reactions show that metal-porphyrin systems are catalytic in the generation of organic molecules from biological material such as sugars, cellular material and cell walls