English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Zendy Plus

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Zendy Tools

Zendy Open

Two sets of complexes of Co-triarylcorrole-bispyridine complexes, Co[TpXPC](py) 2 and Co[Br 8 TpXPC](py) 2 have been synthesized, where TpXPC refers to a meso-tris(para-X-phenyl)corrole ligand with X = CF 3 , H, Me, and OMe and Br 8 TpXPC to the corresponding β-octabrominated ligand. The axial pyridines in these complexes were found to be labile and, in dilute solutions in dichloromethane, the complexes dissociate almost completely to the five-coordinate monopyridine complexes. Upon addition of a small quantity of pyridine, the complexes revert back to the six-coordinate forms. These transformations are accompanied by dramatic changes in color and optical spectra. 1 H NMR spectroscopy and X-ray crystallography have confirmed that the bispyridine complexes are authentic low-spin Co(III) species. Strong substituent effects on the Soret maxima and broken-symmetry DFT calculations, however, indicate a Co II -corrole •2- formulation for the five-coordinate Co[TpXPC](py) series. The calculations implicate a Co(d z 2  )-corrole("a 2u ") orbital interaction as responsible for the metal-ligand antiferromagnetic coupling that leads to the open-shell singlet ground state of these species. Furthermore, the calculations predict two low-energy S = 1 intermediate-spin Co(III) states, a scenario that we have been able to experimentally corroborate with temperature-dependent EPR studies. Our findings add to the growing body of evidence for noninnocent electronic structures among first-row transition metal corrole derivatives.

Electronic Structure of Cobalt–Corrole–Pyridine Complexes: Noninnocent Five-Coordinate Co(II) Corrole–Radical States