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Alkylation of one of the inner‐core nitrogen atoms is one possible approach to obtain dianionic corrole ligands, suitable for the coordination of divalent metal ions, such as PdII. Inner‐core N‐methylation can be obtained by treating the corrole with CH3I, but the reaction conditions should be optimized to limit the formation of the dimethylated derivative. Two regioisomers, the N‐21 and the N‐22 methyl derivatives are obtained from the reaction, with the first product achieved in a higher amount. Structural characterization of the reaction products evidenced the distortion induced by the introduction of the methyl groups; the N‐methylcorroles are chiral compounds, and the enantiomers were separated by chromatography, with their absolute configuration assigned by ECD computation. Palladium insertion was achieved in the case of monosubstituted corroles, but not with the dimethylated macrocycle; X‐ray characterization of the complexes showed the distortion of the macrocycles. The Pd complexes do not show luminescence emission, but are able to produce singlet oxygen upon irradiation. The PdII complexes were also inserted in human serum albumin (HSA) and dispersed in water; in this case, the protein protects the corroles from photobleaching, and a switch from the type II to the type I mechanism in reactive oxygen species (ROS) production is observed. [ABSTRACT FROM AUTHOR]

Porphyrinoids are considered perfect candidates for their incorporation into electron donor–acceptor (D–A) arrays due to their remarkable optoelectronic properties and low reorganization energies. For the first time, a series of subphthalocyanine (SubPc) and corrole (Cor) were covalently connected through a short‐range linkage. SubPc axial substitution strategies were employed, which allowed the synthesis of the target molecules in decent yields. In this context, a qualitative synthetic approach was performed to reverse the expected direction of the different electronic events. Consequently, in‐depth absorption, fluorescence, and electrochemical assays enabled the study of electronic and photophysical properties. Charge separation was observed in cases of electron‐donating Cors, whereas a quantitative energy transfer from the Cor to the SubPc was detected in the case of electron accepting Cors. [ABSTRACT FROM AUTHOR]

This article, titled "Cover Feature: Palladium Complexes of N-Methylcorroles," explores the chirality and coordination chemistry of N-alkylcorroles. The researchers have successfully separated enantiomeric pairs of monoalkylated regioisomers and determined their absolute configuration. The N-alkylation of corroles has a significant impact on their coordination chemistry, allowing for the preparation of divalent ion complexes like PdII. The photophysical properties of N-alkylcorroles show promise for future applications as photosensitizers and catalysts. The full research article provides more detailed information on this topic. [Extracted from the article]

Two synthetic routes for the preparation of the water soluble 5,10,15‐tris(4‐sulfonatophenyl)corrole are reported. The first approach explores the chlorosulfonation reaction on the phosphorus complex of 5,10,15‐tris(4‐trimethylsilylphenyl)corrole. Following this route, the P complex of the target corrole has been obtained in low yields, while the major product was the tetrasubstituted complex, with the additional sulfonyl group regioselectively introduced at the 2‐position. To widen the scope of the reaction, the direct preparation of the 5,10,15‐tris(4‐sulfonatophenyl)corrole has been pointed out, affording both the target corrole and the intermediate chlorosulfonyl derivative in reasonable yields. The photophysical properties and the protonation equilibria of both corroles have been investigated, showing that 5,10,15‐tris(4‐sulfonatophenyl)corrole does not aggregate in acidic solutions, different from the analogous porphyrin. [ABSTRACT FROM AUTHOR]

Two different copper and gallium arylcorroles have been functionalized using the Vilsmeier–Haack reaction. A further Knoevenagel reaction with cyanoacetic acid was performed on both complexes, affording the desired products with yields above 90 %. The newly synthesized compounds have been thoroughly characterized by a combination of spectroscopic methods, optical analyses, and X‐ray crystallography. Moreover, they have been tested as anchoring groups for the hydrothermal synthesis of ZnO nanoparticles. The morphology of the heterogeneous composites has been studied by SEM, EDS and fluorescence microscopy analyses, thus confirming the presence of the corrole macrocycle in the hybrid material. A new class of corrole complexes bearing a cyanoacetic moiety at the β‐position was obtained in excellent yields through a Knoevenagel reaction. The newly prepared compounds were thoroughly characterized and the peripheral carboxylic moiety was used as an anchoring group in the synthesis of ZnO nanoparticles. [ABSTRACT FROM AUTHOR]

An efficient β-functionalization of [5,10,15-tris-(4-methylphenyl)corrolato]cobalt derivatives through a Vilsmeier-type reaction allows the introduction of an acrolein substituent, which is subsequently copolymerized with pure acrolein. The obtained hybrid microspheres are exploited as nanogravimetric chemical sensors. The sensing properties of the developed sensors are tested through exposure to different volatile organic compounds chosen as model analytes. The results show improved sensor sensitivity of the resulting devices for all the tested analytes with respect to sensors functionalized with either corrole or polyacrolein. The enhanced properties are attributed to the accurate and tunable merging of the properties of both exploited materials. [ABSTRACT FROM AUTHOR]