Lawrence Berkeley National Laboratory
Synthesis and Molecular Structure of a Copper Octaiodocorrole.
- Author(s): Thomassen, Ivar K
- McCormick, Laura J
- Ghosh, Abhik
- et al.
Published Web Locationhttps://pubs.acs.org/doi/full/10.1021/acsomega.8b00616
Although rather delicate on account of their propensity to undergo deiodination, β-octaiodoporphyrinoids are of considerable interest as potential precursors to novel β-octasubstituted macrocycles. Presented herein are early results of our efforts to synthesize β-octaiodocorrole derivatives. Oxidative condensation of 3,4-diiodopyrrole and aromatic aldehydes failed to yield free-base octaiodocorroles. Treatment of copper meso-tris(p-cyanophenyl)corrole with N-iodosuccinimide and trifluoroacetic acid over several hours, however, yielded the desired β-octaiodinated product in ∼22% yield. Single-crystal X-ray structure determination of the product revealed a strongly saddled corrole macrocycle with metrical parameters very close to those of analogous Cu octabromocorrole complexes. The compound was also found to exhibit an exceptionally red-shifted Soret maximum (464 nm in dichloromethane), underscoring the remarkable electronic effect of β-octaiodo substitution.