[375-72-4] C4F10O2S (MW 302.11) InChI = 1S/C4F10O2S/c5-1(6,3(9,10)11)2(7,8)4(12,13)17(14,15)16 InChIKey = LUYQYZLEHLTPBH-UHFFFAOYSA-N (mild alkylating reagent for amines and alkoxysilanes; precursor for nonafluorobutanesulfinic and -sulfonic acids and various nonafluorobutyl sulfones) Alternate Name: NfF. Physical Data: bp 65–66 °C/760 mmHg; d 1.682 g cm−3. Solubility: sol ether, THF; insol CH2Cl2. Form Supplied in: colorless to pale yellow liquid of 90% purity; impurities are branched nonafluorobutanesulfonyl fluorides. Analysis of Reagent Purity: 19F NMR;1 MS.2 Preparative Methods: by electrochemical fluorination of alkanesulfonyl halides in anhyd HF at 4–6 V,3 or, better, by electrochemical fluorination of sulfolene.1 Purification: dried over CaCl2 and distilled. Handling, Storage, and Precautions: store in amber colored bottles protected from light; for prolonged storage, PVC bottles are recommended.

The syntheses of the iron azaphthalocyanines Tetra(2,3-pyrido)porphyrazinato-iron, T(2,3-Py)PFe (1), Tetra(3,4-pyrido)porphyrazinato-iron, T(3,4-Py)PFe (2), Tetrapyrazoporphyrazinato-iron, TPzPFe (3), Tetratertbutyltetrapyrazoporphyrazinato-iron tbu[Formula: see text]TPzPFe (4) is reported. They react with the monodentate pyridine, substituted pyridines, piperidine (pip) and various isontriles to form the corresponding bis-axially substituted porphyrazinato-iron compounds McFeL[Formula: see text]. Bidentate ligands. [Formula: see text] pyrazine (pyz) or diisocyanobenzene (dib), form the polymeric adducts, [Formula: see text] [T(2,3-Py)pyz][Formula: see text] or [T(2,3 Py)PFedib][Formula: see text]. The spectroscopic data ([Formula: see text]H-NMR, IR, UV-vis, Mössbauer) are reported and compared with the analogous phthalocyaninato-iron compounds.

The control of luminous radiation has extremely important implications for modern and future technologies as well as in medicine. In this Review, we detail chemical structures and their relevant photophysical features for various groups of materials, including organic dyes such as metalloporphyrins and metallophthalocyanines (and derivatives), other common organic materials, mixed metal complexes and clusters, fullerenes, dendrimeric nanocomposites, polymeric materials (organic and/or inorganic), inorganic semiconductors, and other nanoscopic materials, utilized or potentially useful for the realization of devices able to filter in a smart way an external radiation. The concept of smart is referred to the characteristic of those materials that are capable to filter the radiation in a dynamic way without the need of an ancillary system for the activation of the required transmission change. In particular, this Review gives emphasis to the nonlinear optical properties of photoactive materials for the function of optical power limiting. All known mechanisms of optical limiting have been analyzed and discussed for the different types of materials.

Review: preparation of symmetrical and unsymmetrical mono-; tetra-; and octa-glycosylated zinc phthalocyanines; 42 refs.

GRAPHICAL ABSTRACTExcellent photophysical and photochemical properties completed by magnificent take-up rates in malignant tissues attracted a great deal of interest to the application of glycosylated and glycoconjugated phthalocyanines in photodynamic therapy. In this study we describe the concise synthesis and full characterization of 16 differently 3,6-bisglycoconjugated phthalonitriles 3, 5, 6, 8, and 48–59, which are precursors for a new generation of photosensitizers, namely, nonperipheral glycoconjugated phthalocyanines. The first example for the synthesis of a nonperipheral glycoconjugated zinc phthalocyanine 60 from phthalonitrile 48 is also presented in this work.

In continuation of our work on glycoconjugated phthalocyanines, two new water soluble, non-ionic zinc(II) phthalocyanines have been prepared and fully characterized by means of 1H-NMR, 13C-NMR, MALDI-TOF, ESI-TOF, UV-Vis spectroscopy, emission spectroscopy and fluorescence lifetime measurements. The carbohydrate-containing phthalonitrile precursors were synthesized through a copper-catalyzed azide-alkyne cycloaddition (CuAAC). The 2-methoxyethoxymethyl protecting group (MEM) was used to protect the carbohydrate moieties. It resisted the harsh basic cyclotetramerization conditions and could be easily cleaved under mild acidic conditions. The glycoconjugated zinc(II) phthalocyanines described here have molar extinction coefficents εmax > 105 m−1 cm−1 and absorption maxima λ > 680 nm, which make them attractive photosensitizers for photo-dynamic therapy.

In the first part; the syntheses of mono-; di-; and tetra-glycosylated phthalonitriles is described; which are the most used starting materials for the preparation of the corresponding glycosylated metal (mostly zinc) phthalocyanines. In the second section; the preparation of symmetric and unsymmetric mono-; tetra-; and octa- glycosylated zinc phthalocyanines are reviewed; in which the sugar is attached to the phthalocyanine macrocycle; either anomerically or via another one of its OH-groups.

The review is focused on the current state of the synthesis of glycosylated phthalocyanines and their precursors, mono-, di-, and tetraglycosyl phthalonitriles. Features of the synthesis of phthalogen conjugates with carbohydrates and the formation of related metal phthalocyanine complexes are discussed. The formation of aggregates of phthalocyanines in various media exerts a significant effect on the physicochemical and photochemical properties of phthalocyanine macrocycles, which is especially important in the practical use of phthalocyanines as photosensitizes. An aggregation of phthalocyanine conjugates in aqueous solutions strongly decreases the quantum yield of singlet oxygen, thus diminishing the biological activity of these compounds. Specific features of phthalocyanine conjugate aggregation with carbohydrates in aqueous solutions, organic solvents, and some their mixtures are analyzed.

Herein we present the synthesis and full characterization of the water-soluble [1,4-bis(α,β-galactopyranos-6-yl)phthalocyaninato]zinc(II) (8). For a cross-condensation with phthalonitrile in presence of zinc bromide, bisglycosylated phthalonitrile (5) has been synthesized by nucleophilic displacement of triflyl groups or fluorine atoms by acetonide protected galactose in the appropriated phthalonitriles 1 and 2. Furthermore we prepared 3,6-bis(1,2:3,4-di-O-isopropylidene-α-D-galactopyranos-6-yl)phthalonitrile (5) starting from 2,3-dicyanohydroquinone and 1,2:3,4-di-O-isopropylidene-α-D-galactopyranose using a Mitsunobu protocol. UV-vis spectra of 8 were measured in DMSO, water and PBS-buffer at different concentrations.

Photophysical and photochemical properties of a series of tetra- and octaglycosylated zinc phthalocyanines (ZnPcs) substituted with glucose and galactose moieties have been reported. Spectral properties of these phthalocyanines are compared in DMSO. Absorption spectra of the non-peripherally tetra-substituted ZnPcs 2 showed a significant red shift in their Q-band maxima as compared to the peripherally substituted analog 1 . All the complexes gave high triplet quantum yields ranging from 0.68 to 0.88, whereas triplet lifetimes were in the range of 100–430 µs in argon-saturated solutions. The octagalactosylated ZnPc 3b showed the highest triplet quantum yield and singlet oxygen quantum yield of 0.88 and 0.69, respectively. The fluorescence quantum yields and lifetimes of all the compounds under investigation were within the range of zinc phthalocyanine complexes.

The first part of this review summarizes methods for the syntheses of mono-, di-, and tetra-substituted glycosylated phthalonitriles, which are the main starting materials for the preparation of the corresponding glycosylated metal phthalocyanines. In the second part the preparation of symmetrically and unsymmetrically tetra- and octa- glycosylated zinc phthalocyanines in which the sugar is attached either anomerically or via another one of its OH -groups to the phthalocyanine macrocycle as well as other structurally different glycosylated metal phthalocyanines are reviewed.

1,4,8,11,15,18,22,25-Octafluorophthalocyanato zinc (F8PcZn), which is not described in the literature up to date, was obtained from 3,6-difluorophthalonitrile in anhydrous DMF, DBU, and Zn(OAc)(2) at 145 degrees C. 3,6-Difluorophthalonitrile was synthesized by a multistep procedure.

The valence electronic properties of some unsubstituted and peripherally substituted oxo-titanium phthalocyanines are reported. Semiempirical quantum chemical calculations show that the nature of peripheral substituents has a strong bearing on the valence electronic properties, including the state dipole moments and absorption wavelength. The non-linear optical response was measured around the the Q-band resonance. The effect of different substituents and substitution patterns on the non-linear behaviour of the samples was determined. The combined results suggest that tuning of electronic and optical properties is effectively achieved by functionalization of the edges of the conjugated ring. Copyright (C) 1999 John Wiley & Sons, Ltd.

The octaalkyl- or octaalkoxysubstituted phthalocyaninatogermanium dichlorides 10b,d,e and 10a-c were reacted with bisbromomagnesiumacetylene 16 and bisbromomagnesium-p-diethynylbenzene 18, respectively with formation of the corresponding acetylene bridged oligomers 17a-c and 19a-c, respectively.

The ground state electronic absorption spectra, photophysics and photochemistry of amphiphilic octaglucosylated zinc phthalocyanines containing oxygen or sulfur bridges are presented. Triplet quantum yield values for the two dyes (in DMF and DMSO) vary between 0.71 and 0.84, while singlet quantum yield values lie between 0.63 and 0.75. Fluorescence lifetimes were determined experimentally by time correlated single photon counting and semi-empirically by fluorescence quenching techniques; and values from both methods were within the same range. Kinetic data were obtained for the quenching of the triplet state of the phthalocyanines by ground state molecular oxygen; the bimolecular collisional quenching rate constant range between 2.35 × 108 and 1.13 × 109 M-1.s-1. These values suggest that triplet states of the dyes are effectively quenched by ground molecular oxygen.

In this work we present our new experimental and theoretical results upon investigations of the photoinduced tautomerism processes of single metal-free porphyrin-type molecules. During tautomerization a molecule changes its structure, therefore the excitation transition dipole moment (TDM) of the molecule changes its orientation. Using confocal microscopy in combination with azimuthally and radially polarized laser beams we are able to determine the orientation of the TDM as well as the orientation of a single molecule itself. In the case of tautomerism we are able to visualize this process and even the involved isomers separately. The study first focuses on two symmetrical compounds: a phthalocyanine and a porphyrin. Additionally, differences of the single molecules embedded in a polymer matrix or just spin-coated on a glass cover slide and under nitrogen flow are investigated. In the latter case we observe a higher frequency of the change of the TDM orientation. The experimental studies are supplemented by quantum chemical calculations. Variations of the molecular substituents, the environment and excitation wavelength can give new insights into the excited-state tautomerism process of a single molecule. We also introduce some suggestions for future experiments to support the understanding of the photoinduced tautomerism.

Amorphous hexadecafluoro(phthalocyaninato)ruthenium(II) F16PcRu (1) has been studied with EXAFS spectroscopy. It has been shown that F16PcRu has a dimeric structure in the solid state.

Tautomerism process of single fluorescent molecules was studied by means of confocal microscopy in combination with azimuthally or radially polarized laser beams. During a tautomerism process the transition dipole moment (TDM) of a molecule changes its orientation which can be visualized by the fluorescence excitation image of the molecule. We present experimental and theoretical studies of two porphyrazine-type molecules and one type of porphyrin molecule: a symmetrically substituted metal-free phthalocyanine and porphyrin, and nonsymmetrically substituted porphyrazine. In the case of phthalocyanine the fluorescence excitation patterns show that the angle between the transition dipole moments of the two tautomeric forms is near 90°, in agreement with quantum chemical calculations. For porphyrazine we find that the orientation change of the TDM is less than 60° or larger than 120°, as theoretically predicted. Most of the porphyrin molecules show no photoinduced tautomerization, while for 7% of the total number of investigated molecules we observed excitation patterns of two different trans forms of the same single molecule. We demonstrate for the first time that a molecule, undergoing a tautomerism process stays in one tautomeric trans conformation during a time comparable with the acquisition time of one excitation pattern. This allowed us to visualize the existence of each of the two trans forms of one single porphyrin molecule, as well as the sudden switching between these tautomers.

Several tetra- and octaglycosylated PcZn 's 1a, 2a–2d, 3a-b and 4 were investigated for their aggregation behavior using different concentrations of the PcZn -species in pure DMSO, water and in various DMSO/water mixtures by comparing their UV-vis spectra. The PcZn 's 1–4 are independent of the concentration in pure DMSO and in up to 25 vol.% water/DMSO mixtures are non aggregated. Increasing amounts of water leads to higher aggregation ratios. The aggregation behavior is influenced by the nature and the position of the sugar substituents on the Pc-ring. PcZn 4 was found the least aggregated compound even in pure water.