β-Octabromo- and β-Octakis(trifluoromethyl)isocorroles: New Sterically Constrained Macrocyclic Ligands

Thomas, Kolle E.; Beavers, Christine M.; Gagnon, Kevin J.; Ghosh, Abhik

doi:10.1002/open.201700035

β-Octabromo- and β-Octakis(trifluoromethyl)isocorroles: New Sterically Constrained Macrocyclic Ligands

Journal Article · Fri May 26 00:00:00 EDT 2017 · ChemistryOpen

DOI:https://doi.org/10.1002/open.201700035· OSTI ID:1413727

Thomas, Kolle E. ^[1]; Beavers, Christine M. ^[2]; Gagnon, Kevin J. ^[2]; ^[1]

Arctic Univ. of Norway, Tromso (Norway). Dept. of Chemistry, Center for Theoretical and Computational Chemistry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source

Here, we present a study of the acid-induced demetalation of two sterically hindered copper corroles, Cu β-octabromo-meso-triphenylcorrole (Cu[Br₈TPC]) and β-octakis(trifluoromethyl)-meso-tris(p-methoxyphenyl)corrole (Cu[(CF₃)₈TpOMePC]). Unlike reductive demetalation, which affords the free-base β-octabromocorrole, demetalation of Cu[Br₈TPC] under non- reductive conditions (CHCl₃/H₂SO₄) resulted in moderate yields of free-base 5- and 10-hydroxy isocorroles. The isomeric free bases could be complexed to Co^II and Ni^II, affording stable complexes. Only reductive demetalation was found to work for Cu[(CF₃)₈TpOMePC], affording a highly saddled, hydrated corrole, H₃[5-OH,10-H-(CF₃)₈TpOMePC], where the elements of water had added across C5 and C10. Interaction of this novel free base with Co^II resulted in Co[iso-10-H-[CF₃)₈TpOMePC], a Co^II 10-hydro isocorrole. Finally, the new metal complexes were all characterized by single-crystal X-ray diffraction analysis and, despite their sterically hindered nature, were found to exhibit almost perfectly planar isocorrole cores.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1413727

Journal Information:: ChemistryOpen, Journal Name: ChemistryOpen Journal Issue: 3 Vol. 6; ISSN 2191-1363

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Isocorroles as Homoaromatic NIR-Absorbing Chromophores: A First Quantum Chemical Study Foroutan-Nejad, Cina; Larsen, Simon; Conradie, Jeanet Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-29819-3	journal	August 2018
Rapid one-pot synthesis of pyrrole-appended isocorroles Larsen, Simon; McCormick, Laura J.; Ghosh, Abhik Organic & Biomolecular Chemistry, Vol. 17, Issue 12 https://doi.org/10.1039/c9ob00168a	journal	January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
corroles
isocorroles
macrocyclic ligands
near-infrared
single-crystal x-ray crystallography

CCDC 1532288: Experimental Crystal Structure Determination E., Thomas, Kolle; M., Beavers, Christine; J., Gagnon, Kevin https://doi.org/10.5517/ccdc.csd.cc1nfgn6 The current record is supplemented by this dataset	dataset	January 2021
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CCDC 1532292: Experimental Crystal Structure Determination: VEXPIA : (2,3,7,8,12,13,17,18-octabromo-10-hydroxy-5,10,15-triphenylisocorrole)-(triphenylphosphine)-cobalt(iii) benzene solvate Thomas, Kolle; Beavers, Christine; Gagnon, Kevin https://doi.org/10.5517/ccdc.csd.cc1nfgsb The current record is supplemented by this dataset	dataset	June 2018

β-Octabromo- and β-Octakis(trifluoromethyl)isocorroles: New Sterically Constrained Macrocyclic Ligands

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