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

Zsolt Valicsek, G. Lendvay, O. Horváth

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Hg2 2+ 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 HgII 2P2.

Original languageEnglish
Pages (from-to)910-926
Number of pages17
JournalJournal of Porphyrins and Phthalocyanines
Volume13
Issue number8-9
Publication statusPublished - Aug 2009

Fingerprint

Porphyrins
Mercury
Metals
Metalloporphyrins
Ions
Ligands
Sandwich structures
Dimerization
Charge density
Heavy ions
Anions
Metal ions
Absorption spectra
Nitrogen
Kinetics
Chemical analysis

Keywords

  • B3LYP/LANL2DZ TD-DFT calculation
  • Bisporphyrins
  • Dimercury(I) porphyrins
  • Indirect LMCT
  • Out-of-plane position
  • Photophysics
  • Primary photochemistry
  • Sitting-atop (SAT) characteristics
  • UV-vis spectroscopy

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{12a9af85dced40a398458104bfe14861,
title = "Equilibrium, photophysical, photochemical and quantum chemical examination of anionic mercury(I) porphyrins",
abstract = "Hg2 2+ 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 HgII 2P2.",
keywords = "B3LYP/LANL2DZ TD-DFT calculation, Bisporphyrins, Dimercury(I) porphyrins, Indirect LMCT, Out-of-plane position, Photophysics, Primary photochemistry, Sitting-atop (SAT) characteristics, UV-vis spectroscopy",
author = "Zsolt Valicsek and G. Lendvay and O. Horv{\'a}th",
year = "2009",
month = "8",
language = "English",
volume = "13",
pages = "910--926",
journal = "Journal of Porphyrins and Phthalocyanines",
issn = "1088-4246",
publisher = "Society of Porphyrins and Phthalocyanines (SPP)",
number = "8-9",

}

TY - JOUR

T1 - Equilibrium, photophysical, photochemical and quantum chemical examination of anionic mercury(I) porphyrins

AU - Valicsek, Zsolt

AU - Lendvay, G.

AU - Horváth, O.

PY - 2009/8

Y1 - 2009/8

N2 - Hg2 2+ 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 HgII 2P2.

AB - Hg2 2+ 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 HgII 2P2.

KW - B3LYP/LANL2DZ TD-DFT calculation

KW - Bisporphyrins

KW - Dimercury(I) porphyrins

KW - Indirect LMCT

KW - Out-of-plane position

KW - Photophysics

KW - Primary photochemistry

KW - Sitting-atop (SAT) characteristics

KW - UV-vis spectroscopy

UR - http://www.scopus.com/inward/record.url?scp=70350334614&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=70350334614&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:70350334614

VL - 13

SP - 910

EP - 926

JO - Journal of Porphyrins and Phthalocyanines

JF - Journal of Porphyrins and Phthalocyanines

SN - 1088-4246

IS - 8-9

ER -