Phthalocyanines

ABSTRACT The unsymmetrical binuclear phthalocyanine 4a and the symmetrical binuclear phthalocyanine 4b with two different metals (Ni and Cu), as well as the correspondent binuclear phthalocyanines with two Ni atoms (4c and 4d) were synthesized from the benzoannulated dicyano-substituted Ni phthalocyanine 2. Atomic absorption spectroscopy verified unambiguously the presence of Ni and Cu in the binuclear phthalocyanines. The proposed synthetic route demonstrates great versatility towards substitution at the peripheral positions of the ring and the variation of the chelating central metal. Complexes 4a−4d are soluble in common organic solvents of medium polarity. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

The synthesis and characterization of new phthalocyanines bearing eight N-alkyl or N-aryl sulfonamide groups is described. The synthetic route involves the chorosulfonation of 4,5-diphenoxyphthalonitrile with chlorosulfonic acid and reaction of the resulting 4,5-bis(p-chlorosulfonylphenoxy)phthalonitrile with amines. The sulfonamide-substituted phthalonitriles are then cyclotetramerized to yield the title compounds in good yields (50–83%).

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, 13 C 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.

The synthesis and characterization of the first rigid fused porphyrin-phthalocyanine hetero-dyad with two different metals is reported; was based on porphyrin’s dienophile features in Diels–Alder reactions. This synthetic procedure represents a new approach for the synthesis of extended systems based on tetrapyrrolic macrocycles.

This review gives an overview of the nonlinear transmission (NLT) properties of near-infrared absorbing materials such as naphthalocyanines, extended porphyrins, conjugated polyenes, polymethines and other chromophores. Special attention is given to the mechanism of the NLT effect, discussing the several types mechanisms encountered. It focuses on the most important contributions about materials modulation through organic synthesis versatility, permitting the variation of the different physico-chemical features, and consequently aiming the achievement of effective systems in terms of NLT performance.

Phthalocyanines are excellent photosensitizers for photodynamic therapy as they have strong absorbance in the near infra-red region which is most relevant for in vivo activation in deeper tissular regions. However, most phthalocyanines present two major challenges, ie, a strong tendency to aggregate and low water-solubility, limiting their effective usage clinically. In the present study, we evaluated the potential enhancement capability of glycerol substitution on the photodynamic properties of zinc (II) phthalocyanines (ZnPc). Three glycerol substituted ZnPc, 1-3, (tetra peripherally, tetra non-peripherally and mono iodinated tri non-peripherally respectively) were evaluated in terms of their spectroscopic properties, rate of singlet oxygen generation, partition coefficient (log P), intracellular uptake, photo-induced cytotoxicity and vascular occlusion efficiency. Tetrasulfonated ZnPc (ZnPcS4) was included as a reference compound. Here, we showed that 1-3 exhibited 10-100 nm red-shifted absorption peaks with higher molar absorptivity, and at least two-fold greater singlet oxygen generation rates compared to ZnPcS4. Meanwhile, phthalocyanines 1 and 2 showed more hydrophilic log P values than 3 consistent with the number of glycerol attachments but 3 was most readily taken up by cells compared to the rest. Both phthalocyanines 2 and 3 exhibited potent phototoxicity against MCF-7, HCT-116 and HSC-2 cancer cell-lines with IC50 ranging 2.8-3.2 µM and 0.04-0.06 µM respectively, while 1 and ZnPcS4 (up to 100 µM) failed to yield determinable IC50 values. In terms of vascular occlusion efficiency, phthalocyanine 3 showed better effects than 2 by causing total occlusion of vessels with diameter <70 µm of the chorioallantoic membrane. Meanwhile, no detectable vascular occlusion was observed for ZnPcS4 with treatment under similar experimental conditions. These findings provide evidence that glycerol substitution, in particular in structures 2 and 3, is able to improve the photodynamic properties of ZnPc.

Systematic changes in the exocyclic substitution of a core phthalocyanine platform tune the absorption
properties to yield commercially viable dyes that function as the primary light absorbers in organic bulk
heterojunction solar cells. Blends of these complementary phthalocyanines absorb a broader portion of
the solar spectrum compared to a single dye, thereby improving solar cell performance. We correlate
grazing incidence small angle X-ray scattering data with solar cell performance to elucidate the role of
the nanomorphology of active layers composed of blends of phthalocyanines and a fullerene derivative.
A highly reproducible device architecture is used to ensure accuracy and is relevant to films for solar
windows in urban settings. We demonstrate that the number and structure of the exocyclic motifs
dictate phase formation, hierarchical organization, and nanostructure, thus can be employed to tailor
active layer morphology to enhance exciton dissociation and charge collection efficiencies in the
photovoltaic devices. These studies reveal that disordered films make better solar cells, short alkanes
increase the optical density of the active layer, and branched alkanes inhibit unproductive
homogeneous molecular alignment.

On studying Situation Report of WHO 167 dated 5 July 2020 , Number of confirmed COVID-19 cases, by date of report and WHO region, 30 December through 5 July **SR 167. Length of bar shows Active Viral load on different Races on different dates upto 5 th July. TCNC (total confirmed new caces) shows that viral load is racial dependent. High in American race (yellow) and European Race (orange) , Moderate in Eastern Mediterranean (violet) and South East Asia (blue) and Least in Africa (Green) and western Pacific (mustard) races. TND (Total New Deaths) means doubling time of Covid 19 virus is also racial dependent. Hence the death rate TD/TCC (26 March to 23 May 2020)is high in European race (13.3 %) and minimum in African race (1.35 %). During that period AGE was advocated to deprogram Viral load and Viral doubling time to control death rate in High damage (HD) and Moderate Damage (MD) zones by GCEP (Global Covid Eradication Program launched by UOG. Racial dependent Doubling time of Covid 19 shows that Covid 19 viruses are of different mutants globally like different cancers have different doubling time (decided by TND) and it is decided by divine mechanics. Hence Anti cancers drugs could kill Covid 19 as their dynamics simulate cancer .

This review gives an overview concerning the optical limiting (OL) properties of materials like porphyrins and phthalocyanines. It gives special attention to the phthalocyanine and porphyrin modulation aiming the achievement of effective systems in terms of OL performance through the appropriate combination and modulation of several structural components. The versatility of the methods of organic synthesis here considered permits the variation of the different chemical features, such as the nature of the ring substituents, the central atom, the ligands attached to the central atom and the degree of electronic conjugation of the macrocycle. Previous works on this field are referred, but the more recent developments are emphasised. Review with more than 100 references.

Ternary phthalocyanine–metal–polyoxometalate (Pc–M–POM)
complexes were synthesized and characterized. Group (IV) Hf or
Zr ions reside outside the plane of the macrocycle and are
coordinated to both the phthalocyanine and the lacunary
polyoxometalate. The metal ions mediate the electronic communication between the Pc and the POM.

Two metallosulfophthalocyanines, RuPcS and FePcS, used
in many catalytic oxidation reactions, were readily oxidized
by hydrogen peroxide or monopersulfate, under acidic or
neutral conditions in water, to form novel metal complexes
derived from the facile oxidation of the PcS ring. Meso-nitrogen-
oxide derivatives and metal-biliverdin-like derivatives
were identified among the products at early reaction times,
whereas at longer times fragmentation of the phthalocyanine
ring occurred, with formation of sulfophthalimide and metal
complexes containing the resulting tridentate ligand. The oxidative
degradation of the MPcS complexes has been investigated
by ESI-MS, UV/Vis-NIR and 1H, 13C and 15N NMR
spectroscopy. These rapidly formed, coordinatively unsaturated
complexes represent the dominant species in oxidizing
media, at least in the case of the Ru derivative, and must be
the real catalyst precursors in previously published oxidation
reactions using MPcS complexes. The oxidative degradation
reactions occurred with selective mono-denitrogenation of
one meso-nitrogen atom and formation of ammonia, thus recalling
the celebrated selective degradation of heme to verdoheme
and/or biliverdin and CO.

The nonlinear optical properties of an unsymmetrical Zinc phthalocyanine were studied using the Z-scan technique in femtosecond and picosecond time domains. Open aperture Z-scan studies with∼ 110 femtosecond pulses revealed an intriguing behavior exhibiting switching phenomena (from saturable absorption to reverse saturable absorption and back to saturable absorption) as a function of concentration and the peak intensities used. Similar behavior was observed with∼ 2 picosecond pulse excitation. The observed results are ...

The protruding oxophilic central metal ion of ZrIV
porphyrinoids facilitates axial coordination to the oxygen bearing functional groups on graphene oxide (GO) surfaces to result in new supramolecular photonic materials with high dye loading especially on edges and large defects. The reaction proceeds at room temperature with GO dispersed in tetrahydrofuran and GO films on glass. Since the ZrIV serves as a conduit, the photophysical properties of the dye sensitized GO derive from both the axially bound chromophores and the GO substrate. Self-organization of metalloporphyrinoids on GO mediated by axial coordination of group (IV) metal ions allows for direct sensitization of graphene and graphenic materials without requiring covalent chemistries with poorly conducting linkers.

The goal of this work was to investigate the photodynamic activity of 5,10,15,20‐tetrakis[4‐(3‐N,N‐dimethylaminopropoxy)phenyl]chlorin (TAPC) and zinc(II) 2,9,16,23‐tetrakis[4‐(N‐methylpyridyloxy)]phthalocyanine iodide (ZnPPc4+) as photosensitizers to inactivate Staphylococcus aureus biofilms and prevent their formations in different culture media.
Methods: We incubated S aureus biofilms in different culture media: tryptic soy (TS),
nutrient (N), Müeller Hinton (MH) broth, TS with glucose 2 and 5% (w/v) with 5 μM
ZnPPc4+ or TAPC and irradiated with visible light (350‐800 nm). Photodynamic inactivation (PDI) was determined by count of colony forming units (CFU) and crystal violet method. Furthermore, we studied PDI effect on biofilm development in TS broth.
Finally, we examined the effects of PDI on the structure of S aureus biofilm.
Results: Greater inactivation was achieved, using TAPC or ZnPPc4+, when S aureus
biofilm was grown in N or MH broths rather than in TS. Besides, glucose addition to
the medium decreases the ability to develop biofilm and increase the photoinactivation
capacity. Prevention of 3 log biofilm developments was obtained when S aureus
cultures were treated with TAPC (10 μM) and 108 J/cm2 in TS broth and the number
of CFU was counted after 24 hours. Moreover, microscopy studies demonstrated
modifications in biofilm architecture.
Conclusions: These results indicate that TAPC and ZnPPc4+ may be promising photosensitizers for photodynamic inactivation of S aureus biofilms or to prevent their
formation.

... I Desulfurization of thiopyrimidine or thiopurine nucleosides with dimethyldioxi-rane alone or in the presence of an amine led to various N-or 0-derivatives like M-cytidine, N6 and C8-adenosine derivatives (Scheme 16).120.121 The first direct aminolysis of 2-thiouracil ...

—Carbon 3D structures were obtained by spray pyrolysis using toluene solution containing suspended nickel or magnesium phthalocyanines as precursors of metallic particles serving as catalysts for carbon phase formation. The process was conducted in a range of temperatures in a quartz tube in inert atmosphere on borosilicate glass supports where the nanometric layers of nanoparticles were deposited. The samples were analyzed by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Infrared Spectroscopy Fourier Transform (FTIR) and Raman spectroscopy; their condusctivity was measured via Kelvin technique. The properties of formed nanolayers were analyzed according to metal nature in the phthalocyanine, temperature, carrier gas speed, and other process parameters. Possible MEMS applications of thus fabricated nanolayers are discussed.

This novel research opens the possibility of controlling the spectral, fluorescent and non-linear optical (NLO) properties of stable J-type phthalocyanine dimers. In our group, thermally and chemically stable supramolecular J-type dimers, based on low-symmetry phthalocyanine macrocycles, have been synthesised for the first time, and the present work is a fruitful continuation of the initiated studies. Using an example of a dimeric magnesium complex, consisting of the same anti-parallel oriented 2-hydroxy-9,10,16,17,23,24-hexabutylphthalocyanine macrocycles, we first demonstrated the ability of stable phthalocyanine J-dimers to undergo peripheral functionalisation. UV-Vis, fluorescence and DFT studies showed that when 2-(diethylphosphoryl)-4-methylpenta-1,3-dienyl-3-oxy-moieties are introduced into a dimer structure, the intermolecular association of large molecules varies significantly, tending to ordering. Simulation of the nonlinear optical properties with the TDHF/6-311++G** theoretical approximation has shown that the chemical alteration of a dimeric structure results in an increasing polarisability (a), first hyperpolarisability (b) and an angle q(m,b max) between the dipole moment m and the main direction of the charge-transfer transition b max .