Equilibrium, photophysical, photochemical and quantum chemical examination of anionic mercury(I) porphyrins

Abstract

Hg22+ion and 5,10,15,20-tetrakis(parasulphonato-phenyl)porphyrin anion can form 2:1 (2 clusters:1 porphyrin) and 2:2 complexes, while the formation of the 1:1 species is not observable: it is only an intermediate, similarly to the cases of other large metal ions of small charge-density. The differences between mercury(I) and mercury(II) porphyrins in the composition of monoporphyrins (2:1 vs. 1:1), in the stability and the Soret absorption based on the arrangement of 2:2 complexes (asymmetric vs. probably symmetric sandwich-structure), in the kinetic behavior (molecularities and the special dimerization of HgIIP4-), in the product of the photoinduced dissociations of 2:2 bisporphyrins (free-base ligand vs. 1:1 complex) can prove that no mercury(II) porphyrins can form due to the possible disproportion of dimercury(I) ions. However, the similarities in the absorption, photophysical and photochemical features (also to other out-of-plane metalloporphyrins) suggest that the out-of-plane position of metal center and the distorted structure of complexes may be responsible for these common properties, the so-called sitting-atop characteristics. Moreover, the calculated structural data of the theoretically studied 1:1 mercury(I) porphyrin are very similar to those of HgIIP as a consequence of the charge separation in the cluster based on the strength of metal-nitrogen bonds. In the case of the 2:2 species, neither the increased distance (because of the Hg-Hg bond), nor the absence of 45° rotation of the two ligands can significantly modify the π-π interaction because its both measured and calculated absorption spectra are similar to those of HgII2P2.