Application of the electronic spectra of porphyrins for analytical purposes: the effects of metal ions and structural distortions
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Tartalom: http://real.mtak.hu/50823/
Archívum: MTA Könyvtár
Gyűjtemény: Status = Published



Type = Article
Cím:
Application of the electronic spectra of porphyrins for analytical purposes: the effects of metal ions and structural distortions
Létrehozó:
Valicsek, Zsolt
Horváth, Ottó
Kiadó:
Elsevier
Dátum:
2013
Téma:
QD01 Analytical chemistry / analitikai kémia
QD02 Physical chemistry / fizikai kémia
QD03 Inorganic chemistry / szervetlen kémia
Tartalmi leírás:
We investigated the UV-Vis absorption, singlet-1 and singlet-2 fluorescence, as well as the formation of several metalloporphyrins from equilibrial and kinetic aspects in aqueous solution. Among these complexes were numerous typical out-of-plane and several in-plane metalloporphyrins, and between the two categories, a few border-line cases. On the basis of our results, we have complemented the categorization introduced by Barnes and Dorough for the metalloporphyrins. According to our observations, also in metalloporphyrins, the distortion, i.e., the planarity or nonplanarity of the macrocycle, is basically responsible for the spectral characteristics, while the electronic structure of metal center is a secondary factor, with a considerable importance mainly in the in-plane complexes. The type of complexes can be spectrophotometrically determined on the basis of their UV-Vis absorption and fluorescence spectra. Beside the spectral and photophysical effects of metalation, also those of the structural distortions were studied, which can originate also from metalation, protonation or overcrowded peripheral substitution of the free-base porphyrins, as well as from the axial ligation of metalloporphyrins.
Our observation may be useful for different spectrophotometric analytical detection and determination methods, e.g. size-selective metal detection using free-base porphyrins (or other ringed chelate ligands), as well as the determination of Lewis bases as potential axial ligands, using metalloporphyrins.
Nyelv:
magyar
Típus:
Article
PeerReviewed
info:eu-repo/semantics/article
Formátum:
text
Azonosító:
Valicsek, Zsolt and Horváth, Ottó (2013) Application of the electronic spectra of porphyrins for analytical purposes: the effects of metal ions and structural distortions. Microchemical Journal, 107. pp. 47-62. ISSN 0026-265X
Kapcsolat:
https://doi.org/10.1016/j.microc.2012.07.002