Journal of Porphyrins and Phthalocyanines

Two metal-free porphyrins H${}_2$Pp (a, b) and four metalloporphyrins CuPp (a, b) and ZnPp (a, b) have been applied to lithium/thionyl chloride (Li/SOCl${}_2)$ battery as the high efficient catalysts for the first time. Notably, the battery discharge time in blank is only 1080 s while that of Li/SOCl₂ battery after adding porphyrin/metalloporphyrins is 1980 s for H${}_2$Pp (a), 2160 s for H${}_2$Pp (b), 1560 s for CuPp (a), 1320 s for CuPp (b), 1620 s for ZnPp (a), and 1680 s for ZnPp (b), respectively. Furthermore, the energy of the battery whose electrolyte contains the H${}_2$Pp (a, b), CuPp (a, b) and ZnPp (a, b) increases by approximately 11.88–77.14% than that of the battery without them. And the metal-free porphyrins H${}_2$Pp (a) or H${}_2$Pp (b) exhibit higher catalytic activities than that of metalloporphyrins CuPp (a, b) and ZnPp (a, b). In addition, the possible reasons to explain the excellent results were also analyzed.

Using a hydrothermal reaction of SmCl₃•6H₂O, ZnBr₂ and TPPS, a crystalline metalloporphyrinic compound (MPC), [SmZn(TPPS)H₃O]${}_n$•2$n$H₂O (1), was synthesized. The crystal structure of the MPC exhibits a condensed and robust 3-D porous open framework. We studied the adsorption and desorption isotherms for N₂, H₂ and CO₂ conducted at 77 K and 273 K. They show different isotherms such as Type I, II and III isotherm behaviors. We found that low temperature is propitious for the title complex to adsorb more H₂, but less N₂. Compound 1 showed remarkably high selectivity for CO₂–N₂ separation, and good thermal stability. The temperature dependent magnetic susceptibility shows an antiferromagnetic-like behavior for 1.

In the present research meso-tetrakis(4-carboxyphenyl)porphyrinatomanganese(III) acetate (Mn(TCPP)OAc) nanoparticles have been prepared for the first time without any stabilizing agent or supporting matrix under ultrasonic irradiation. Scanning electron microscopy (SEM) was used to characterize and investigate the nanocatalyst. Rapid, efficient, facile and highly selective oxidation of a wide range of olefins by tetra-$n$-butylammonium hydrogen monopersulfate over the prepared manganese nanocatalyst was investigated. Also oxidation of sulfides and alkanes in the presence of the (Mn(TCPP)OAc) nanoparticles were studied. The catalyst is recovered by filtration and reused at least five times.

Seven A₃- and trans-A₂B manganese(III) corroles (1–7-Mn) differing widely in their electronic and steric features were synthesized and transformed to their corresponding $\beta$-brominated manganese(III) corroles derivatives (1a–7a-Mn). Their corresponding (oxo)manganese(V) corroles 1–7-Mn(oxo) and 1a–7a-Mn(oxo) were further prepapred by treating with iodosylbenzene (PhIO). The reactivity for the oxygen atom transfer from 1–7-Mn(oxo) to styrene followed the order of 1-Mn(oxo) > 2-Mn(oxo) > 7-Mn(oxo) > 4-Mn(oxo) > 3-Mn(oxo) > 6-Mn(oxo) $\approx$5-Mn(oxo). The same pattern was observed for their $\beta$-brominated analogs 1a–7a-Mn(oxo), albeit their reactivity was remarkably higher. The steric protection of ${\mathrm{\text{Mn}}}^{\mathrm{\text{V}}}\equiv \mathrm{\text{O}}$ moiety by ortho–ortho′-dibromophenyl substituents was found to enhance the stability of (oxo)manganese(V) corroles significantly.

Three mono-fluorine substituted porphyrin compouds were synthesized under microwave irradiation. The effects of catalysts and oxidants on the yields of mono-fluorine substituted porphyrins also were investigated. The yields of 5,10,15,20-tetrakis(4-fluorophenyl)porphyrin, 5,10,15,20-tetrakis(3-fluorophenyl)porphyrin, 5,10,15,20-tetrakis(2-fluorophenyl)porphyrin in a use of nitrobenzene in propionic acid were 36%, 30% and 28%, respectively. In addition, the zinc(II) ion incorporation reactions into porphyrins to form the zinc porphyrin complexes have been kinetically investigated in acetic acid.

The crystallization and the crystal and molecular structure of a very slightly soluble electrostatically interacting pair of porphyrins is described. The tetra-anion 5,10,15,20-tetrakis-(4-sulfonatophenyl)-21,23H-porphyrin [H₂TPPSO₃]${}^{4-}$ and the tetra-cation 5,10,15,20-tetra($N$-methylpyridyl)21H,23H-porphyrin [H₂TMePyP]${}^{4+}$ are found to form an alternating one-dimensional stack that is stabilized by electrostatic interactions between the porphyrin rings but also by $\pi –\pi$ interactions between all substituted phenyl rings in the ensemble. The resulting interactions between the porphyrins is exceptionally tight.

The magnetocaloric effect (MCE), heat capacity, and magnetization thermodynamic parameters of the high-spin (octakis-trifluoromethylphenyltetraazaporphinato)manganese(III) acetate, (AcO)MnTAP(3-CF₃C₆H${}_4{)}_8$, in a 1% aqueous suspension were determined by means of microcalorimetric method at 275–320 K in magnetic fields of 0.1–1.0 T. The conditions are comparable with those used with (octakis(3-tert-butylphenyl)tetraazaporphinato)manganese(III) acetate, (2,3,7,8,12,13,17,18-octaethylporphinato)manganese(III) chloride and (5,10,15,20-tetraphenylporphinato)manganese(III) chloride, acetate or bromide studied earlier. Paramagnetic properties were found in high-disperse particles of complexes, positive MCE values were obtained. As paramagnets, these complexes exhibit a big magnetocaloric effect (up to 0.85 K when the magnetic induction is changed from 0 to 1 T) at temperatures close to room, what could be employed for cooling in home and industrial refrigerators and hyperthermia in cancer diagnostics and therapy. MCE sensitivity to the nature and electronic structure of the aromatic macrocycle was discussed. The specific heat capacity of the complex depended on the temperature was obtained. Effect of magnetic field on the temperature dependence of the specific heat capacity for (AcO)MnTAP(3-CF₃C₆H${}_4{)}_8$ practically is not visible.

Porphyrin macrocycles play an important role in designing of fluorophores with superior light harvesting properties similar to that of antennas in biological systems. In this paper, new Zn(II)porphyrin dyes were investigated to improve the performance of the YD2-o-C8 using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. Effects of various substituted and anchoring groups on basic porphine and Zn(II)porphyrin derivatives were systematically studied at the B3LYP/LanL2DZ level. The absorption spectra of Zn(II)porphyrin derivatives bearing one, two and four anchoring groups in the meso-positions were also studied. The calculations showed that a molecule [5, 10, 15, 20-(4-carboxyphenylethynyl)porphyrinato]Zn(II) have large absorption cross-section than available in the existing porphyrin dyes. The results of these calculations would open up enormous possibilities to develop porphyrin dyes characterized by high absorption cross-section for various light harvesting applications.

Two platinum porphyrins, meso-tetramesitylporphyrinatoplatinum and meso-tetrakis(pentaflourophenyl) porphyrinatoplatinum, are explored for catalytic application in the selective oxidation of sulfide to sulfoxide by iodosylbenzene. The obtained overall turnover number of 90,000 in the oxidation of thioanisole in the presence of meso-tetrakis(pentaflourophenyl) porphyrinatoplatinum indicates the pronounced catalytic activity of the platinum porphyrins. Perfect selectivity toward sulfoxide or sulfone also was achieved via stoichiometric control of reactants.