Journal of Porphyrins and Phthalocyanines

The paper reviews the development of the chemistry, properties and applications of 1,4,8,11,15,18,22,25- (or non-peripheral) octasubstituted phthalocyanines that has been undertaken at the University of East Anglia over the last quarter of a century. The research has proved valuable for initiating and developing a number of areas of phthalocyanine science, not least because the compounds exhibit a number of properties seldom shared by Pc derivatives with other substitution patterns. In particular the compounds are obtained isomerically pure and the substituents' location at the non-peripheral sites as opposed to the peripheral positions ensures superior solubility and lower aggregation in most hydrophobic solvents. A further significant difference between isomeric non-peripheral (np)- and peripheral (p)-octasubstituted compounds is the effect of substituents on the energy of the Q-band, those at the former positions leading to more significant bathochromic shifts of this absorption band into the near infra-red. Examples of np-octasubstituted derivatives exhibit columnar mesophase behavior, a property shared by their p-octasubstituted counterparts. The favorable solubility of the np-octasubstituted compounds, including examples in which one of the four benzenoid rings bears different substituents from those on the other three (so called AAAB structures), in organic solvents facilitates their deposition as thin film formulations. A high degree of molecular organisation within Langmuir-Blodgett (LB) films of amphiphilic AAAB compounds has been investigated using various methods. Spin-coated films of certain AAAA and AAAB series of compounds have been shown to contain layer structuring and purpose designed AAAB compounds have been used in formation of self-assembled monolayers (SAMs). The use of LB and spin-coated films within electrical devices is described. Various applications of SAMs deposited on gold surfaces have been explored including gas sensing. Recent attention has focused on their use, when deposited onto gold nanoparticles, for applications in PDT, an approach complementing more conventional PDT studies. The principal challenge for obtaining the np-octasubstituted compounds is in preparing the precursor phthalonitriles. Though 3,6-dialkoxyphthalonitriles are readily prepared, early access to the 3,6-dialkylphthalonitriles was somewhat laborious. However, more convenient syntheses of the latter are now available through metal catalyzed cross-coupling reactions. Interesting contrasts in the reactivity of 3,6-dialkylphthalonitriles and 4,5-dialkylphthalonitriles have been uncovered. Thus reactions of the former with excess lithium in alcoholic solvents or with excess MeMgBr provide particularly ready access to examples of macrocycles that are hybrids of the Pc and tetrabenzoporphyrin structures. This level of reactivity is very different among the 4,5-dialkylphthalonitriles. Unexpectedly limited reactivity of np-octahexylsubstituted Si(OH)₂Pc in condensation reactions has been exploited to provide a basis for the stepwise construction of m-oxo linked hetero-chromophore arrays. Finally, the unexpected construction of the novel EPR active Cd₂Pc₃ complexes from both np- and p-octaalkyl substituted CdPcs provided examples where both series behaved similarly – in contrast to behavior exhibited by alternatively substituted CdPcs investigated to date.

Photodynamic therapy (PDT) is a promising treatment for cancer that has been recently accepted in the clinic. In this study, we examined a biological significance of PDT with a chlorin-based photosensitizer, Photodithazine, on cervical cancer model. When human papillomavirus type 16 (HPV16)- transformed mouse TC-1 cells were exposed to varied doses of Photodithazine with light irradiation (6.25 J/cm²), the significant growth inhibition of TC-1 cells was observed at 0.75 μg/mL of Photodithazine. The damaged cells by Photodithazine/PDT were categorized to be early and late apoptosis, as determined by annexin V staining. Photodithazine was primarily localized at lysosome apparatus within TC-1 cells while it was rapidly accumulated and sustained for initial 3 h in tumor tissue of TC-1 tumor bearing mice after IV injection. The tumor growth inhibition by Photodithazine/PDT with light irradiation (300 J/cm²) was examined after injection of various concentration of Photodithazine in tumor mice system. Our results show that Photodithazine/PDT might have significant advantages in the selective killing of tumor lesions in HPV 16 E6/E7 associated cervical cancer model, both in vitro and in vivo.

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.

Three manganese biscorrole dyads were synthesized, physicochemically characterized and investigated as to their electrochemistry and spectroelectrochemistry in nonaqueous media. Each dyad contained the same two corroles linked in a face-to-face arrangement via one of the three different linking groups, 9,9-dimethylxanthene, anthracene or diphenylether, the exact nature of which determined the distance and possible interaction between the two metallomacrocycles. The initial compounds contained Mn(III) in their air stable form and were shown to exhibit two major redox processes, one being a Mn(III)/Mn(IV) conversion and the other being either Mn(III)/Mn(II) or reduction at the conjugated macrocycle to give a Mn(III) corrole π-anion radical when the solvent was pyridine. The potentials and reversibility of each electron transfer reaction were shown to depend upon the solvent (pyridine, CH₂Cl₂, or PhCN), type of spacer separating the two macrocycles and/or the presence or absence of axial ligation. The site of each electron transfer was assigned on the basis of spectroscopic and electrochemical data and by comparison with reactions and properties of the monocorrole (Mes₂PhCor)Mn which was characterized in a previous publication and also examined in the current study under the same solution conditions as the newly investigated dyads. Some electrode reactions of the dyads were followed by coupled chemical reactions and these were also elucidated in the present study.

5-(8-ethoxycarbonyl-1-naphthyl)-10,15,20-triphenyl porphyrin (ENTPP) has been synthesized in a one-pot reaction, and the corresponding chiral crystalline samples have been obtained by spontaneous resolution. ¹H NMR spectrum suggests it is mononaphthyl substituted species and an ethyl group is over the porphyrin plane. The structure has been further confirmed by X-ray crystallography. ENTPP·C₆H₁₄ (C₅₇H₅₀N₄O₂): monoclinic, P2₁, a = 10.707(2) Å, b = 12.203(2) Å, c = 17.858(4) Å, β = 103.06(3)°, V = 2272.8(8) ų, Z = 2. The 8-position substituent, ester group, lies above the porphyrin plane and leads to the conformational chirality. The entire structure is built up with homochiral molecules, which leads to a chiral crystal through packing in P2₁ space group. Circular dichroism (CD) spectra have exhibited remarkable absorptions in the Soret band region, which further confirms the homochirality of the crystalline samples.

In the present work, explicit water molecule and solvent-field effects on the absorption spectrum of chlorophyll a have been studied using time-dependent density functional theory (TDDFT) method. Calculated results show that the one complex and two water coordinated complexes formed by concerted coordination and hydrogen-bonding interactions would be the most preferable conformations of chlorophyll a in aqueous surroundings. Moreover, four obvious absorption bands are assigned by comparing the theoretically simulated absorption spectra with the experimental ones. The theoretical study shows that the explicit water molecule interactions slightly influence the first absorption band. However, the water coordination and hydrogen-bonding interactions can significantly affect the second absorption band which has a strong red-shift. The solvent-field effect due to the polarity of water on absorptions in Q-bands is relatively smaller than that on absorptions in B-bands. As a consequence, our theoretical study on the absorption spectra in the 350–400 nm region presents that the absorption strength in this region was influenced by the explicit coordination and hydrogen bonding interactions from water molecules, significantly.

A mild green and efficient approach for hydrogen peroxide oxidative converting oximes to the corresponding carbonyl compounds with a water-soluble manganese porphyrin as catalyst in water/acetone mixture has been developed. The water-soluble manganese porphyrin showed an excellent activity for the oxidative deoximation reactions of various oximes under ambient conditions in the absence of any additive. The oxidative deoximation was through the formation of high valent oxo-manganese species, which was confirmed by in situ UV-vis spectroscopy.