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Tetra-2,3-pyridoporphyrazinatosilicon (SiPyD) containing bis(tri-n-hexylsiloxy) (1) or bis(n-heptylcarbonyloxy) (2) axial ligands have been prepared and characterized by NMR, IR and electronic absorption spectroscopies and by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). These SiPyDs are soluble in common organic solvents, and face-to-face-type stacking is prevented in solution and films. Accordingly, their NMR spectra could be reasonably assigned. Their electronic absorption spectra in solution appear to the blue and red compared with those of the corresponding Si phthalocyanines (SiPcs) and Si tetrapyrazinoporphyrazines (SiPyZs) respectively. These characteristics are reproduced by molecular orbital calculations in the framework of the Pariser-Parr-Pople approximation. On formation of films, the Q bands shift to the red of those in solution by ca 20 nm, suggesting that other similar tetravalent metallophthalocyanines with two long axial ligands can be used for shifting the Q band to the red. TGA and DTA experiments show that the thermal stability of the macrocycles is markedly influenced by the type of axial ligands.

Novel Zn(II) phthalocyanine and naphthalocyanine DBU complexes have been prepared in a one-pot synthesis reacting phthalonitrile precursors with an excess of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). For the first time, it has been well evidenced that DBU played the role of coordinating axial ligand together with the well known role of strong base. Also, DBU complexes showed better solubility in organic solvents due to the coordination of the bulky axial DBU ligand, compared to the Zn(II) phthalocyanines and naphthalocyanines without coordinated DBU. The coordinating properties of DBU toward ZnPcs (DBU free) complexes have also been investigated along with the ZnPc(pyridine) complex. Thermal analysis results reflecting the stability of the synthesized complexes under air are also presented.

The synthesis of various axially substituted titanium phthalocyanines in high yield using microwave irradiation without an added solvent is reported. The times of reaction, as expected, are short and generally less than 10 minutes. The products were obtained in high purity after chromatography.

Mn(III)-tetra phenyl porphyrin-acetate (MnTPPOAc) and some kinds of meso-phenyl substituted porphyrins by hydroxyl groups and their Mn(III) complexes were synthesized. These Mn-porphyrins were used as catalyst in the epoxidation of various alkenes with tetra-n-butylammonium hydrogen monopersulfate (n-Bu₄NHSO₅) as oxidant and tetra-n-butylammonium acetate (n-Bu₄NOAc) as the axial ligand. The following order of catalytic activity was observed for cyclooctene: T(2,3-OHP)PMnOAc ≫ T(2,4,6-OHP)PMnOAc ≥ T(4-OHP)PMnOAc ≥ T(2,6-OHP)PMnOAc ≥ TPPMnOAc and T(2,3-OHP)PMnOAc ≫ TPPMnOAc > T(4-OHP)PMnOAc > T(2,4,6-OHP)PMnOAc > T(2,6-OHP)PMnOAc for other alkenes. Different activity and stability of the catalysts were interpreted based on the hydrogen bonding between hydroxyl groups with appropriate orientation on the meso-position of the phenyl groups and axial bases or oxidant. T(2,3-OHP)PMnOAc catalyst has shown optimal condition for effective hydrogen bonding. In the case of other catalysts, electronic and steric factors overcome the hydrogen bonding effect.

Various nitrogenous bases, such as imidazoles, pyridines and amines were employed as axial ligands in epoxidation reaction of cyclooctene bytetra-n-butylammonium hydrogen monopersulfate (n-Bu₄NHSO₅), in the presence of Mn(III)-tetrakis(2,3-dimethoxyphenyl)porphyrin-acetate (T(2,3-OMeP)PorMnOAc). T(2,3-OMeP)PorMnOAc is a fairly stable catalyst, with the ability of producing hydrogen bonding. High epoxidation yield of 85 ± 6% was obtained in the presence of imidazole axial ligand with 100% selectivity in 30 min. Higher conversion of around 100% was obtained by pyridine axial base, while selectivity was reduced to 69%. Further epoxidation reactions were also performed using Mn(III)-Tetrakis(2,3-dihydroxyphenyl)porphyrin-acetate (T(2,3-OHP)PorMnOAc) as catalyst. In addition to the usual electronic and steric effects, it is proposed that the catalytic activity depends on the existence and kind of hydrogen bonding between the axial base and the ortho-methoxy or hydroxy groups on the phenyl rings of manganese porphyrin. The cis to trans ratio of cis-stilbene oxide formed by imidazole and pyridine axial bases were obtained as 7.5 and 2.5 respectively. In addition GC-Ms and UV-vis studies were employed to find the nature of active species and product formation. Our DFT calculations disclosed that pyridine hydrogen bonding with moiety of the macrocycle rings strongly affects the relative energies of S/Q spin states in [T(2,3-OMeP)PorMn^V(O)(Py)]⁺, in that it results in the longer Mn–O bond and reactivity toward substrates.

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${}_{\mathrm{\text{4}}}$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${}_{\mathrm{\text{2}}}$. Bidentate ligands. $e.g.$ pyrazine (pyz) or diisocyanobenzene (dib), form the polymeric adducts, $e.g.$ [T(2,3-Py)pyz]${}_{\mathrm{\text{n}}}$ or [T(2,3 Py)PFedib]${}_{\mathrm{\text{n}}}$. The spectroscopic data (${}^{\mathrm{\text{1}}}$H-NMR, IR, UV-vis, Mössbauer) are reported and compared with the analogous phthalocyaninato-iron compounds.

Phthalocyanines (Pcs) are near-infrared photosensitizers with therapeutic potential for the treatment of bacterial infections and cancer. However, their clinical utility has been hindered by poor solubility in biological fluids, lack of specificity, and limited clearance from affected tissues. Glycosylated Pcs have the potential to overcome these issues by providing increased solubility and tumor specific targeting. However, reliable methods for their synthesis remains challenging. Here we present our first approach towards the synthesis of a series of silicon (IV) phthalocyanine conjugates bearing axial carbohydrate ligands (CPcCs). The novelty of our approach lies in the installation of axial alkyne ligands which can be functionalized with readily accessible acetyl protected azido glycosides, thus providing a modular approach for the synthesis of these complex macromolecules.

Manganese porphyrins are of interest due to the optical, electronic and magnetic properties of the central metal ion, coupled to the low bandgap of the polyaromatic ring. These attractive characteristics are harnessed in solutions or in ultra-thin films, such as, for example, self-assembled monolayers. However, for devices, thicker films deposited using a controlled and reproducible method are required. Here we present the morphological, structural, chemical and optical properties of manganese(III) tetraphenylporphyrin chloride (MnTPPCl) thin films deposited using organic molecular beam deposition, typically employed to process analogue molecules for applications such as organic photovoltaics. We find, using a combination of UV-vis and X-ray photoelectron spectroscopies, that the sublimation process leads to the scission of the Mn–Cl bond. The resultant film is a Mn(II)TPP:Mn(III)TPPCl blend where approximately half the molecules have been reduced. Following growth, exposure to air oxidizes the Mn(II)TPP molecule. Through quantitative analysis of the time-dependent optical properties, the oxygen diffusion coefficient (D) $\sim 1.9\times 10^{-17}{\mathrm{\text{cm}}}^2/\mathrm{\text{s}}$ is obtained, corresponding to a slow bulk oxidation following fast oxidation of a 8-nm-thick surface layer. The bulk diffusion D is lower than for analogous polycrystalline films, suggestion that grain boundaries, rather than molecular packing, are the rate-limiting steps in oxidation of molecular films. Our results highlight that the stability of the axial ligands should be considered when depositing metal porphyrins from the vapor phase, and offer a solvent-free route to obtain reproducible and smooth thin films of complex materials for engineering film functionalities.

Phthalocyanines (Pcs) are near-infrared photosensitizers with therapeutic potential for the treatment of bacterial infections and cancer. However, their clinical utility has been hindered by poor solubility in biological fluids, lack of specificity, and limited clearance from affected tissues. Glycosylated Pcs have the potential to overcome these issues by providing increased solubility and tumor specific targeting. However, reliable methods for their synthesis remains challenging. Here we present our first approach towards the synthesis of a series of silicon (IV) phthalocyanine conjugates bearing axial carbohydrate ligands (CPcCs). The novelty of our approach lies in the installation of axial alkyne ligands which can be functionalized with readily accessible acetyl protected azido glycosides, thus providing a modular approach for the synthesis of these complex macromolecules.

Manganese porphyrins are of interest due to the optical, electronic and magnetic properties of the central metal ion, coupled to the low bandgap of the polyaromatic ring. These attractive characteristics are harnessed in solutions or in ultra-thin films, such as, for example, self-assembled monolayers. However, for devices, thicker films deposited using a controlled and reproducible method are required. Here we present the morphological, structural, chemical and optical properties of manganese(III) tetraphenylporphyrin chloride (MnTPPCl) thin films deposited using organic molecular beam deposition, typically employed to process analogue molecules for applications such as organic photovoltaics. We find, using a combination of UV-vis and X-ray photoelectron spectroscopies, that the sublimation process leads to the scission of the Mn–Cl bond. The resultant film is a Mn(II)TPP:Mn(III)TPPCl blend where approximately half the molecules have been reduced. Following growth, exposure to air oxidizes the Mn(II)TPP molecule. Through quantitative analysis of the time-dependent optical properties, the oxygen diffusion coefficient (D) ~1.9 × 10^-17 cm²/s is obtained, corresponding to a slow bulk oxidation following fast oxidation of a 8-nm-thick surface layer. The bulk diffusion D is lower than for analogous polycrystalline films, suggestion that grain boundaries, rather than molecular packing, are the rate-limiting steps in oxidation of molecular films. Our results highlight that the stability of the axial ligands should be considered when depositing metal porphyrins from the vapor phase, and offer a solvent-free route to obtain reproducible and smooth thin films of complex materials for engineering film functionalities.