Metal-centered X-ray absorption and emission spectroscopy of iron corroles: implications for ligand non-innocence - Chemical Science (RSC Publishing) DOI:10.1039/D6SC00669H

The subject of #noninnocent ligands has long been of interest in our labs. We have been particularly interested in defining the phenomenon more rigorously, both theoretically and experimentally. Here’s our latest contribution, pertaining to iron #corrole complexes. pubs.rsc.org/en/content/a...

The video is up in YouTube! CASSCF with ORCA, merging metal and ligand fragment wavefunctions to retrieve all metal 3d orbitals.
#compchem #chemsyk #CASSCF #Corrole #ORCA

youtu.be/LAm9jEFDjKM

8 viales with solutions ranging from purple to green to brown, from different corroles.

This is not red cabbage! These are all #corrole solutions! Beautiful colours made by Gianella at our lab! #realtimechem #chemsky #science

Computer screen showing a scanning electron micrograph of a large conglomerate of spherical nanoparticles made of PLA and a chromophore.

The work I did Tuesday washing and resuspending our polymer/corrole nanoparticles was well worth it! Some of the pictures were quite nice and I learned a lot! #corrole #nano #photodynamictherapy #chemsky #science

Crystals of a corrole under magnifying glass. The solution looks light pink, possibly due to fluorescence, and the crystals are dark purple, needle like

These are #crystals of another free base #corrole (different from the one I posted before). Now two different compounds are traveling to the crystallographer! Awesome work by UG student Gianella. #chemsky #chemistry #science

Photos of small corrole crystals seen through magnifying glass. The solutions is purple and the crystals are very dark purple.

So happy about these unmetallated #corrole crystals. About to send them to my crystallographer friend! #realtimechem #chemsky

Rhenium-Sulfido and -Dithiolato Corroles: Reflections on Chalcophilicity 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.

Is rhenium oxophilic or thiophilic? It’s both, almost equally. Check out our new creations – #rhenium-sulfido #corrole complexes – and some reflections on chalcophilic interactions in @InorgChem pubs.acs.org/doi/10.1021/...