Octaiodoporphyrin

Abstract

Interaction of 3,4-diiodopyrrole with 4-trifluoromethylbenzaldeyde under carefully optimized, Lindsey-type conditions at -10 °C has led to the synthesis of the first β-octaiodoporphyrin, H2[I8TpCF3PP]. The free ligand readily yielded Ni, Cu, and Zn complexes, which all proved amenable to single-crystal X-ray structure analyses. The zinc complex Zn[I8TpCF3PP] exhibits the most saddled porphyrin core for any simple porphyrin known to date and a dramatically red-shifted optical spectrum with a Soret maximum at 495 nm.

Chirogenesis in Zinc Porphyrins: Theoretical Evaluation of Electronic Transitions, Controlling Structural Factors and Axial Ligation

“…This is in agreement with the conclusion of Guberman‐Pfeffer et al [58] . and Thomassen et al [59] . that non‐planarity accounts only in part for the observed shift.…”

Supramolecular Chirogenesis in Bis-Porphyrin: Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative

“…The obtained crystal structure was used as a starting point for further geometry optimization. Three standard protocols were used as follows: (1) refining only the positions of hydrogens and fluorine atoms [74,75], (2) full optimization in the gas phase [74,[76][77][78], and (3) full optimization in dichloromethane (COSMO solvent model) [76,77,79,80]. Optimization was performed using the RI-PB86-3D/def2-SV(P) level of theory followed by further simulation of the UV-Vis and CD spectra by using the ωB97X-D/cc-pVDZ level of theory with the SMD solvent model (see Figure 6 and Table S2 The UV-Vis spectra calculated on the basis of the crystal structure (λmax at 391 and 399 nm) and optimized geometries (λmax at 401 and 415 nm) are blue shifted in comparison to the experimentally obtained spectrum (λmax at 426 and 437 nm) (Figure 6A).…”

Synthesis and Molecular Structure of a Copper Octaiodocorrole

“…Accordingly, we turned our attention to the iodination of copper tris( para -X-phenyl)corrole complexes, Cu[T p XPC], where X = OMe, Me, CF 3 , and CN. 3 Periodic acid/iodine (H 5 IO 6 /I 2 ), which we previously used to iodinate N -triisopropylsilylpyrrole, 6 proved too harsh, resulting in destruction of the Cu corrole. Attempts at metal–halogen exchange on the Cu β-octabromocorroles with n -BuLi or Rieke magnesium, 14 followed by exposure to an iodinating agent, such as N -iodosuccinimide (NIS), proved similarly futile.…”

“…Some progress, however, has taken place recently. Thus, we have recently reported a number of β-octaiodoporphyrin 6 derivatives and Gross and co-workers have reported several polyiodocorrole derivatives. 7−9 The latter group has also reported a facile copper-catalyzed transformation of gold β-iodocorroles to the corresponding β-trifluoromethyl derivatives.…”