Synthesis and coordination studies of 5-(4′-carboxyphenyl)-10,15,20-tris(pentafluorophenyl)porphyrin and its pyrrolidine-fused chlorin derivative

Abstract

An efficient strategy was developed to obtain carboxyphenyl porphyrin, chlorins and metal complexes, with potential applications in photonics and biology.

Synthesis of chlorins and bacteriochlorins from cycloaddition reactions with porphyrins

“…In a previous work, detailed structural analysis of the meso-aryl rings motion in related unsymmetrical pyrrolidine-fused chlorins, including 62 and 63, using NMR, UV spectroscopy and DFT theoretical calculations were reported. 71 In 2018, Silva et al 72 used the reaction of the azomethine ylide AZ1 with 5-(4-methoxycarbonylphenyl)-10,15,20-tris(pentafluorophenyl)porphyrin 64 to obtain the corresponding pyrrolidine-fused chlorin derivative 66 after hydrolysis of the ester group (Figure 19). A microwave irradiation protocol, using acetonitrile as solvent, was applied to obtain a series of metal complexes [Fe(III), Cu(II) and Zn(II)] from 64 and also the pyrrolidinefused chlorin metal complexes from 66 (Fe66, Cu66, Zn66).…”

Biomimetic Oxidation of Benzofurans with Hydrogen Peroxide Catalyzed by Mn(III) Porphyrins

“…The oxidation of benzofurans by hydrogen peroxide was evaluated in the presence of the second generation manganese(III) catalysts presented in Figure 2a and referred to from now on as CAT I, II, and III. Neutral Mn(III) porphyrins I and II were prepared by a microwave procedure in eco-sustainable conditions using nonhazardous solvents [32,33]. The catalytic reactions were carried out at room temperature with acetonitrile as the reaction solvent and in the presence of a co-catalyst that mimics the proton-donating amino acids in the active site of CYPs ( Figure 2b) [10].…”

“…grades and acquired from Fisher Chemicals (Waltham, MA, USA). The manganese porphyrins were prepared using literature procedures [32,33,35]. The chromatographic purifications were carried out using silica gel 60 F 254 from Merck.…”

Ohmic heating-assisted synthesis and characterization of Zn(ii), Cu(ii) and Pd(ii) complexes of heterocyclic-fused chlorins

“…2). 33,34 Ohmic heating (ΩH) is a highly energy-efficient heating process, in which the reaction mixture itself serves as an electrical resistor and it is heated by passing a high frequency (typically 25 kHz) AC electric current through it. The heat is generated in situ in a fast and uniform regime thanks to the motion of the charged species and dipole orientation in solution.…”

“…Despite its importance in chemical synthesis, to date, the synthesis of metal complexes has not been explored under the ΩH process. Having formerly established an efficient procedure for the synthesis of several metallochlorins as potential PSs using microwave irradiation, 33 we now present our results regarding the synthesis of pyrrolidine-and isoxazolidine-fused metallochlorins with different Zn(II), Cu(II) and Pd(II) salts, using ΩH (Scheme 1). The spectroscopic properties of the resulting metallochlorins were investigated by 1 H and 19 F NMR, EPR, ESI mass spectrometry, and UV-Vis and fluorescence spectroscopy, and their thermal behaviour was investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) of the pyrrolidine-and isoxazolidine-fused metallochlorins.…”