Main-group coordination-driven porphyrins (MGCPs) are an emerging class of complexes featuring central main-group elements. Bis-boron(III) B2OF2-porphyrinoids, including porphyrins and corroles, exhib...

We report the synthesis, crystal structure, and spectroscopic and computational electronic-structural characterization of two copper corroles, [Cu(5,15-bis(4-methylcarboxyphenyl)-10-(2-methylcarboxyphenyl)corrole)] (1Cu) and [Cu(5,15-bis(4-nitrophenyl)-10-(2-methylcarboxyphenyl)corrole)] (2Cu), as well as spectroscopic and computational studies on the corrole ligands (H3L1 and H3L2) in their neutral and anionic forms. We have found that the anionic corroles containing the 4-nitrophenyl substituents in positions 5 and 15 of the corrole ring show hypercorrole behavior, where the Q-bands are considerably more intense and red-shifted compared to those in the 4-methylcarboxyphenyl-substituted corroles. Electronic structure calculations using wave function methods (CASSCF/NEVPT2) reveal that the intense Q-bands, which extend slightly into the NIR region, are charge-transfer bands from the anionic corrole core to the strongly electron-withdrawing 4-nitrophenyl substituents. We further show that 2Cu can be reduced indirectly in the presence of excess F– or OH–, and the Q-band shifts toward the red in the polar environment containing the corresponding salts. Our study provides examples of easy-to-prepare anionic corroles, metalated and unmetalated, that show hypercorrole behavior and NIR absorption, and thus could find use in hyperthermal processes.

Chemical reduction of [CoIII(py)2(TPC)] (TPC = trianion of 5,10,15-triphenylcorrole) with one or two molar equivalents of KC8 or Na(Hg) generates the reduced cobalt corrolate species, [CoII(TPC)]− and...

Following the successful synthesis of rhenium-oxido, rhenium-imido, and rhenium-sulfido corroles, a series of para-X-substituted rhenium-selenido triarylcorroles (X = OCH3, CH3, H, F, CF3) have been p...

We report the synthesis, crystal structure, spectroscopic and computational electronic structural characterization of two copper corroles, [Cu(5,15-bis(4-methylcarboxyphenyl)-10-(2-methylcarboxyphenyl...

Porphyrinoids are suitable sensitive materials for potentiometric electronic tongues. In this paper, we take advantage of these properties to develop an electronic tongue using an extended-gate field-effect transistor as a signal transducer. The sensitive films were made of different porphyrins and corroles electropolymerized in situ onto laser-induced graphene electrodes. The electronic tongue was duly characterized with respect to ascorbic acid, a common natural antioxidant. The sensors were shown to be sensitive and selective with respect to common interferents, such as dopamine and uric acid. Finally, the sensors were tested to detect ascorbic acid in artificial tears.