Narrow Results

The synthesis of new Zn(II), and Si(IV) phthalocyanine (Pc) derivatives containing chalcone group was successfully achieved and the compounds were characterized by MALDI-TOF mass spectroscopy, FT-IR, ¹H NMR, ${}^{13}$C NMR, and UV-vis spectral data. The photophysical and photochemical properties of these novel Pcs were investigated in DMF. The in vitro cytotoxic effect of the compounds on mammary breast adenocarcinoma cell lines (MCF-7 and MDA-MB-231) and normal mammary breast epithelium (MCF-12A) were evaluated by using the WST assay. Based on the WST assay analysis, cytotoxicity of the Pc derivatives to mammary breast carcinoma cells was compared to normal mammary breast epithelium cells dependent on light illumination. The results of the present investigation demonstrate that all the Pc derivatives containing the chalcone group have a phototoxic effect on mammary breast cancer cells and could be promising photodynamic therapy (PDT) agents for further studies.

A series of oxacalix[4]arene-linked cofacial bisporphyrins 2–4 have been synthesized as free-bases, biszinc(II) and biscopper(II) complexes. UV-vis, fluorescence and cyclic voltammetric studies were performed on the bisporphyrins. Little electronic interactions between the two porphyrin macrocycles in both the metal-free and biszinc(II) complexes 2 and 3 were observed, while enhanced electronic communications were observed in the case of 4 bearing two copper(II) metal ions. Geometry optimizations were carried out using HF/CEP-31G methods to investigate the molecular structures of these bisporphyrins. Solvent effects on the photophysical properties of these bisporphyrins are also discussed.

The five possible non-peripherally substituted zinc(II) phthalocyanines with different molecular symmetries (Pc1–Pc5) were synthesized from statistical condensation of the phthalonitrile derivatives (A and B). 2-[2-(2-ethoxyethoxy)ethoxy]-1-[2-((2-ethoxyethoxy)-ethoxy)ethoxymethyl]ethyloxy and 2′-[(tert-butoxycarbonyl)amino]ethoxy groups were used as substituents. The structures of the new compounds were characterized using elemental analysis and spectroscopic data including IR, ¹H and ¹³C NMR, electronic absorption and mass spectra. The photophysical and photochemical properties of these new compounds were investigated in DMSO. The effect of the molecular symmetry of phthalocyanine molecules on the photophysical and photochemical properties was compared in this study.

In this study, the photophysical, nonlinear absorption and nonlinear optical limiting properties of zinc and gallium phthalocyanine complexes: tetrakis[(benzo[d]thiazol-2-yl phenoxy)phthalocyaninato]zinc(II) (3), tetrakis[(benzo[d]thiazol-2-yl phenoxy)phthalocyaninato] gallium(III) chloride (4), tetrakis[(benzo[d]thiazol-2-ylthio)phthalocyaninato] zinc(II) (5), tetrakis[(benzo[d]thiazol-2-ylthio)phthalocyaninato] gallium(III) chloride (6), were investigated both in solution and when embedded in polystyrene thin films using 532 nm laser excitation at 10 ns pulses. It was also observed that complexes that have higher triplet state absorption also possessed enhanced nonlinear and optical limiting behavior. Superior optical performance was observed when the complexes were embedded in thin films compared to when they are in solution. Complex 6 in thin films gave the highest imaginary third-order susceptibility (I${}_{\mathrm{\text{m}}}$[X${}^{\mathrm{\text{(3)}}}$]) and hyperpolarizability ($\gamma )$ at 4.61 × 10${}^{\mathrm{\text{-7}}}$ esu and 3.44 × 10${}^{\mathrm{\text{-26}}}$ esu, respectively, with a low I${}_{\mathrm{\text{lim}}}$ value of 0.06 J.cm${}^{\mathrm{\text{-2}}}$

In order to improve the efficacy of photochemical properties for photodynamic therapy (PDT) applications, carboxylic acid groups axially conjugated with silicon(IV) and at the peripheral position with zinc(II) phthalocyanine skeletons for new photosensitizers to investigate the influence of the COOH group positions on the photophysicochemical performance are described in this study. Silicon (IV) (3 and 5) and zinc (II) (7) phthalocyanines were characterized by UV-vis, FTIR, ¹H-NMR, MALDI-TOF MS and elemental analysis spectral data. Furthermore, the photophysical (fluorescence quantum yields and fluorescence quenching studies), photochemical (photodegradation and singlet oxygen generation) and aggregation properties of the newly synthesized phthalocyanines were investigated in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) solutions. The results were compared with that of zinc and silicon phthalocyanines. Singlet oxygen quantum yields ranged from 0.23 to 0.63 via Type II mechanism under the experimental conditions studied. The fluorescence of the phthalocyanine complexes (3, 5 and 7) is effectively quenched by 1,4-benzoquinone (BQ) in DMSO, DMF and THF.

Targeting biotin receptors in cancer cells can improve specifying of photosensitizers (PSs) for cancer treatment by photodynamic therapy (PDT) applications. Consequently, there has been extensive research focusing mainly on the design of PSs with optimized pharmaceutical properties and better targeting toward cancer cells. Herein a tailored mono-biotinylated zinc(II) phthalocyanine (Pc-1) substituted with six phenoxy-bis(triazolyl) substituents has been synthesized. This Pc-1 has been further modified to its cationic version (Pc-2) through quaternizing of the triazole moiety to gain water solubility. Both non-ionic zinc(II) phthalocyanine (Pc-1) and its cationic derivative (Pc-2) were characterized by standard spectroscopic techniques, namely; FT-IR, ¹H and ${}^{13}$C NMR, UV-Vis and MALDI-TOF, and by elemental analysis. The photophysical and photochemical properties were evaluated in DMSO for the non-ionic Pc-1 and in both DMSO and water for the cationic Pc-2.

Tetra substituted peripheral and non-peripheral Zn(II) phthalocyanines were successfully synthesized employing 4-(bis(3-methyl-1H-indol-2-yl)methyl)phenol as a starting material. The structure of these synthesized compounds was confirmed using ¹H NMR, ${}^{13}$C NMR, infrared (IR), UV-vis, and MALDI-TOF spectral data. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation) properties of all synthesized peripheral and non-peripheral compounds were investigated in order to determine the potential of these compounds for application in photodynamic therapy.

New borondipyromethene (BODIPY) derivatives chelated at the boron centre with different catecholate and salicylate ligands were synthesized via substituting the fluoride atoms with the aid of aluminum chloride that activates the boron-fluoride bond for substitution. The photophysical properties of the novel BODIPYs were investigated by normalized UV-vis absorption as well as the fluorescence emission spectra. Moreover, the fluorescence quantum yields of the chelated BODIPYs were also calculated and the ultraviolet irradiation of the salicylate derivatives was studied.

A series of $\beta$-pyrrole functionalized push-pull BODIPYs BDP 1-06 were designed and synthesized via Palladium-catalyzed Suzuki cross-coupling reaction and by increasing the oxidation state of the sulfur atom in the thiazine ring. The effect of various donor entities on the photophysical, electrochemical, thermal, and computational studies of the BODIPY was investigated. The absorption spectra of the push-pull BODIPY BDP 2 show a red shift compared to the rest of the BDPs, due to strong donor-acceptor interaction. The phenothiazine-5,5-dioxide functionalized BODIPY BDP 6 exhibit a blue shift in the UV-vis region compared to the phenothiazine substituted BODIPY BDP 5 due to the weak donor ability of the phenothiazine-5,5-dioxide unit. The electrochemical studies were performed for the push-pull BODIPYs BDP 1–6 to analyze the effect of different donor groups on the redox properties of the BODIPY. The thermogravimetric analysis of the BODIPYs BDP 1–6 shows that BDP 2 exhibits excellent thermal stability compared to BDP1, 3, 4, 5, and 6. The theoretical studies reveal that the phenothiazine-5,5-dioxide substituted BODIPY BDP 6 exhibits a large HOMO–LUMO gap compared to phenothiazine functionalized BODIPY BDP 5 due to the low donor ability of the phenothiazine-5,5-dioxide unit. The theoretical calculations were consistent with the experimental observations.

This study delineates the synthesis and comprehensive characterization of metal complexes of meso-tetrakis(pentafluorophenyl)porphyrin (H₂TPF${}_{20}$P, 1) with first-row transition metal ions (M = Mn(III) 2, Fe(III) 3, Co(II) 4, Ni(II) 5, Cu(II) 6, and Zn(II) 7) to elucidate their structural, electronic spectral, and electrochemical redox properties. Co, Ni, Cu and Zn Complexes exhibit planar structure ($\mathrm{\Delta }$24 = 0.003-0.021 Å and $\mathrm{\Delta }$C${}_{\beta }$ = 0.004−0.041 Å) which is also confirmed by the single crystal data of complex ZnTPF${}_{20}$P, 7 shows the planar geometry, while Fe and Mn complexes show the slightly nonplanar structure ($\mathrm{\Delta }$24 = 0.101–0.143 Å and $\mathrm{\Delta }$C${}_{\beta }$ = 0.080–0.112 Å), which are distorted due to their occupied axial sites by −Cl ligand as revealed by density functional theory (DFT) calculations. Furthermore, electronic spectroscopy revealed a gradual bathochromic shift following the order of NiTPF${}_{20}$P < CoTPF${}_{20}$P < CuTPF${}_{20}$PCl < H₂TPF${}_{20}$P = FeTPF${}_{20}$PCl < ZnTPF${}_{20}$P < MnTPF${}_{20}$PCl by appending different metal ions in the porphyrin core. MnTPF${}_{20}$PCl exhibited the most significant bathochromic shift ($\mathrm{\Delta }{\lambda }_{\text{max}}$ = 63 nm) in the Soret band compared to H₂TPF${}_{20}$P. Also, MnTPF${}_{20}$PCl and FeTPF${}_{20}$PCl show a unique pattern of split Soret band at around 364 and 345 nm due to the interaction between the metal $d$-orbitals and the surrounding ligands. The electrochemical redox potentials of the filled 3d orbital of Zn endow ZnTPF${}_{20}$P (ring centered) with the lowest oxidation potential.

Targeting biotin receptors in cancer cells can improve specifying of photosensitizers (PSs) for cancer treatment by photodynamic therapy (PDT) applications. Consequently, there has been extensive research focusing mainly on the design of PSs with optimized pharmaceutical properties and better targeting toward cancer cells. Herein a tailored mono-biotinylated zinc(II) phthalocyanine (Pc-1) substituted with six phenoxy-bis(triazolyl) substituents has been synthesized. This Pc-1 has been further modified to its cationic version (Pc-2) through quaternizing of the triazole moiety to gain water solubility. Both non-ionic zinc(II) phthalocyanine (Pc-1) and its cationic derivative (Pc-2) were characterized by standard spectroscopic techniques, namely; FT-IR, ¹H and ¹³C NMR, UV-Vis and MALDI-TOF, and by elemental analysis. The photophysical and photochemical properties were evaluated in DMSO for the non-ionic Pc-1 and in both DMSO and water for the cationic Pc-2.

This paper uses a novel terpyridine-based dye (4′-(4-2-[dimethyl4,4′-(phenylazanediyl) dibenzoate]phenyl)-2,2′:6′,2′′-terpyri-dine(L)) to synthesize a novel cobalt(II) complex. The complex’s photophysical properties are investigated experimentally using infrared (IR) spectra, UV-vis absorption spectra and photoluminescence (PL) spectra. Moreover, the reliability of the extracted signal is demonstrated to be a more sensitive sensor for the detection of biomolecules in solutions of varying pH.