Journal of Porphyrins and Phthalocyanines最新文献

A series of inner core $N$-alkylcorroles were synthesized and characterized. The introduction of both linear and branched alkyl groups was achieved, demonstrating the quite large scope of the reaction. Polyalkylation results in the formation of the $N$-21,$N$-22 regioisomer, although the introduction of the second alkyl group is less facile than previously observed in the case of the methyl substituent. Complete functionalization of the inner core nitrogens has been investigated, but only the N,N${}^{\prime }$,N${}^{\mathrm{\prime \prime }}$-trimethyl derivatives were obtained. The characterization of these species demonstrated a different arrangement of the methyl groups to the macrocyclic plane, which is peculiar when compared with the conformation of the analogous porphyrin derivatives. These $N$-alkylcorroles should prove to be of potential interest as ligands for various metal ions.

The six coordinated Co^IIIoxophlorin have been studied with imidazole, pyridine and t-butylcyanide as axial ligands using B3LYP, BV86P and MO6-2X methods. Conversion between two isomers [(L)₂Co^III(PO)]${}^{†}$ and [(L)₂Co^III(PO)]${}^{\left|\right|}$ can be occurred at various spin multiplicities, namely singlet, triplet and quintet states. L is employed to show axial ligand namely, imidazole or pyridine. London forces have a basic role in the stability of the mentioned complexes due to non-specific solvent effects. The latter fact has been obtained using the PCM model. Also, it is specified that minimum geometries have not been obtained for some parallel or perpendicular six-coordinated complexes with special axial ligands at a finite spin state. The B3LYP method indicates that one and three $\alpha$-electron can be found on the Co atom in every optimized complex at triplet and quintet spin states, respectively. Also, another $\alpha$-electron is placed on the ring of oxophlorin. This fact is obtained for different isomers of [(IM₂(Co^III(PO)] and [(Py)₂Co^III(PO)] at triplet and quintet spin states, while these complexes are optimized using B3LYP. Besides, results obtained from B3LYP show that the most stable state for six coordinated Co^IIIoxophlorin with any axial ligand is the singlet state. Based on crystal field theory and molecular orbital theory, electron configuration and hybridization of cobalt in [(IM)₂Co^III(PO)] at singlet state can be written as t₂g⁶ eg⁰ and sp³d², respectively. Former electronic configuration indicates a strong field with low spin for d orbitals of cobalt, and latter hybridization is expected for a metal with a coordination number of 6 in a complex with O_h symmetry. The results obtained are completely satisfied by NBO analysis.

A novel 5,10,15,20-tetrakis-(4-(triazol-1-yl)phenyl)porphyridine compound, namely, Zn[5,10,15,20-tetrakis-(4-(triazol-1-yl)phenyl)porphyridine] (hereafter tagged as 1) was synthesized through a solvothermal reaction with mixed solvents at 413 K. The X-ray single-crystal structure of compound 1 is featured as a two-dimensional (2D) layer-like structure with the zinc ion located at the center of the 5,10,15,20-tetrakis-(4-(triazol-1-yl)phenyl)porphyridine. The macrocycle of the 5,10,15,20-tetrakis-(4-(triazol-1-yl)phenyl)porphyridine is coplanar. The zinc ion has six coordination and coordinates with three porphyridines. The photoluminescence spectra of compound 1 with DMF solution reveal that it shows upconversion red photoluminescence. The time-dependent density functional theory (TDDFT) calculation confirms that this upconversion red photoluminescence originated from the MLCT process (metal to ligand charge transfer). The CCT (Correlated Color Temperature) is 2200 K and the CIE (Commission Internationale de I’Éclairage) chromaticity coordinate is (0.6311, 0.3595) for compound 1. The UV-vis diffuse reflectance curve measured with a solid state sample reveals that compound 1 possesses a 2.75 eV band gap.

A novel “on-off-on” switches fluorescence sensor based on TSPP-gallic acid (GA) for S${}^{2-}$-detecting was designed in this article. 5,10,15,20- (4-sulphonatophenyl) porphyrin (TSPP) was synthesized by a modified “one-pot” method. The synthesized TSPP was used as a fluorescence probe for the construction of a fluorescence sensing system. At room temperature, the maximum fluorescence emission wavelength could be obtained at 642 nm when the excitation wavelength was 515 nm when the fluorescence signal was in the “on” mode. The TSPP solution appeared pink in color at this moment. When GA was introduced into the TSPP solution, the fluorescence signal was turned off (fluorescence intensity was quenched) due to the protonation of TSPP, which was caused by the weak acidity of GA. The color of the TSPP solution changed from pink to green. Following that, an acid-base reaction between S${}^{2-}$and GA was initiated when S${}^{2-}$was introduced into the TSPP-GA system, leading to the liberation of TSPP and restoration of fluorescence intensity. The solution color reverted to red, indicating that the fluorescence sensing system had returned to the “on” mode. The TSPP-GA system had good selectivity and sensitivity to S${}^{2-}$, the linear range was 4.52 × 10${}^{-6}$ M $\sim$ 4.34 × 10${}^{-4}$ M, and the detection limit (LOD) was 0.87 $\mu$M. It could be used to detect sulfur ions in actual samples with satisfactory recoveries and RSD values.

A saddle-distorted and cationic Zn(II)-porphyrin complex was revealed to exhibit solvatochromism in organic solvents, depending on the donor numbers. The color change was derived from the alteration of the HOMO-LUMO gap caused by the distortion of the porphyrin mean plane due to solvent coordination.

This review presents typical examples of porphyrins, which serve as highly effective building blocks, primarily drawn from our past achievements. They function as both an electron donor and an energy donor/acceptor in various applications. These applications include photosynthetic and solar cell models, dye-sensitized solar cells, bulk heterojunction solar cells, and optogenetics based on photoinduced charge separation. Consequently, porphyrins are essential components for evaluating energy and electron transfer properties, as well as for energy and biological applications.

This work demonstrated the preparation and characterization of a novel 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) derivative containing boronic acid group and investigation of its non-invasive/non-enzymatic fluorescence sensor behavior for determination of glucose. The novel BODIPY derivative bearing boronic acid pinacol ester (BODIPY-1) was synthesized by Sonogashira coupling reaction between Iodo-BODIPY and 4-ethynylphenylboronic acid pinacol ester. The target novel BODIPY-2 compound which was used as a fluorescence probe for the determination of glucose was synthesized from BODIPY-1 by changing the pinacol ester group to the boric acid moieties. The fluorescence intensity of the BODIPY-2 fluorophore decreased when it interacted with the glucose. Sensing performance towards to glucose of this probe was evaluated in detail concerning the suitable solvent, linear concentration range, convenient pH, limit of detection (LOD), limit of quantification (LOQ) and selectivity. The LOD value of BODIPY-2 was found 0.19 mM toward glucose. Also, the complex stoichiometry between the BODIPY-2 and glucose molecules was determined by Job’s plot technique.

An octahydroxylated photosensitizing Zn phthalocyanine has been used as an initiator in ring-opening polymerization of $𝜀$-caprolactone. Three different phthalocyanine-core star polymers have been obtained, with each arm functionalized with either 20, 30, or 40 units. To benefit from the absorption of these polymers in the first near-infrared (NIR) phototherapeutic window, the phthalocyanine cores have been self-encapsulated into their polycaprolactone arms to yield biocompatible star polymeric nanoparticles exhibiting a remarkable absorption centered at 782 nm and an excellent logarithmic extinction coefficient value in water.

Herein, two porphyrins with bismuth metal incorporated in the porphyrinic core were synthesized having peripheral carboxyl and hydroxyl functional groups. The successful synthesis of free base porphyrin and their bismuth-integrated metalloporphyrins was identified using ¹H NMR spectroscopy, UV-visible and Fourier transform infrared (FT-IR). Further, these bismuth porphyrins complexes were doped with thermally reduced graphene oxide (TRGO) via simple solvothermal techniques. The intrinsic characteristics of prepared metalloporphyrins-based reduced graphene oxide nanocomposites were examined by using various spectroscopic techniques like, photo-physical properties (UV-Visible spectroscopy and Fluorescence spectroscopy), Fourier transform infrared (FT-IR), powdered X-ray diffraction (P-XRD) patterns, FE-SEM and EDX analysis. At last, the photocatalytic properties of nanocomposites were demonstrated by photocatalytic degradation of industrial pollutant rhodamine B (Rh-b) on irradiation of visible light. The catalytic efficiency of RGO-Bi-P1 and RGO-Bi-P2 came out to be 94.58% and 93.26%, respectively.

Two novel porphyrin liquid crystals were designed and synthesized. Their structures were characterized by NMR, FT-IR, UV-visible, and mass spectroscopies. The liquid crystalline properties were investigated by DSC, POM and XRD analyses. The C${}_{12}$ and C${}_{18}$ alkyl chains porphyrin iron(III) complex (1-2) displayed three liquid crystalline transitions in a wide temperature range. Both long alkyl chain porphyrin iron(III) complexes were exhibited a columnar mesophase type.