Spectra, equilibrium and photoredox chemistry of tri- and tetraiodoplumbate(II) complexes in acetonitrile

O. Horváth, Ildikó Mikó

Research output: Contribution to journalArticle

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Abstract

The stepwise formation constant of the kinetically labile PbI4 2 complex was determined in acetonitrile (K4 = 27 ± 4 dm3 mol -1). The lowest-energy bands in the absorption spectra of the tri-and tetraiodoplumbate (II) complexes are attributed to ligand-to-metal charge transfer transitions. Photolysis of these complexes in solution results in the formation of Pb(I) and I or I2 as primary products. The quantum yield of this reaction is 0.1 ± 0.005 for both complexes at 355-nm excitation. The efficiency of the overall reaction (with the formation of I3 - as end product) is higher for the PbI3 1 than for the PbI4 2 complexes (Φ3 = 0.026 ± 0.002 and Φ4 = 0.010 ± 0.004) in air-saturated system. λirr = 366 nm, CPb(11) = 1 X 10 -4 mol dm 3) due to the different repulsion towards the negatively charged reactants. The overall quantum yield is essentially determined by the competitive dark reactions of the primary products, mostly by those of I2. One key step in the mechanism is the reaction between the I2 - intermediate and the ground-state lead(II) complexes, with rate constants of 3.4 ± 1.1 × 107 dm3 mol-1 s-1 and 7.0 ± 2.0 × 107 dm3 mol-1 s-1 at 37 and 94 partial molar percentages of PbI3 -, respectively.

Original languageEnglish
Pages (from-to)95-101
Number of pages7
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume114
Issue number2
Publication statusPublished - Apr 15 1998

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Quantum yield
Acetonitrile
acetonitrile
chemistry
Photolysis
Band structure
Ground state
Charge transfer
Absorption spectra
Rate constants
products
Lead
Metals
Ligands
Air
energy bands
photolysis
charge transfer
absorption spectra
ligands

Keywords

  • Photoredox
  • Tetraiodoplumbate(II)
  • Triiodoplumbate(II)

ASJC Scopus subject areas

  • Bioengineering
  • Physical and Theoretical Chemistry

Cite this

Spectra, equilibrium and photoredox chemistry of tri- and tetraiodoplumbate(II) complexes in acetonitrile. / Horváth, O.; Mikó, Ildikó.

In: Journal of Photochemistry and Photobiology A: Chemistry, Vol. 114, No. 2, 15.04.1998, p. 95-101.

Research output: Contribution to journalArticle

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