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.

The high-temperature (∼180 °C) reaction between free-base meso-triarylcorroles and Re2(CO)10, followed by exposure to PCl3 and thiols (or elemental sulfur), affords rhenium-sulfido (ReS) corroles in 67–76% yields. The use of shorter reaction times, lower temperatures (∼130 °C), and a dithiol (e.g., ethane-1,2-dithiol) also allows the isolation of rhenium-dithiolato corroles, presumptive intermediates on the path to ReS corroles. The ReS corroles exhibit high thermal stability and two reversible oxidations and reductions in their cyclic voltammograms, with redox potentials nearly identical to those observed for analogous ReO corroles. The electrochemical HOMO–LUMO gaps of the complexes, at 2.2 eV, are consistent with ligand-centered oxidation and reduction. The UV–vis spectra of ReS corroles, on the other hand, differ significantly from those of their ReO counterparts. Scalar-relativistic DFT calculations suggest that this difference reflects low-energy LUMO+2 and LUMO+3 levels, consisting of Re–S π-antibonding interactions; the ReO corroles, in contrast, exhibit a larger LUMO+1/LUMO+2 gap, as expected for a relatively classical Gouterman-type metalloporphyrin analogue. The high stability of ReS corroles is consistent with geochemists’ view of rhenium as a moderately chalcophilic element (i.e., one that partitions into sulfide melts) as well as with a recent quantitative analysis of thiophilicity, which indicates that rhenium’s oxophilicity and thiophilicity are essentially evenly balanced.

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...

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...

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...

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.