NDLI: Reactions of Ag<sup>I</sup> ions in alcohols after radiolysis at 77 K

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Reactions of Ag^I ions in alcohols after radiolysis at 77 K

Content Provider	Royal Society of Chemistry (RSC)
Author	Symons, Martyn C. R. Janes, Robert Stevens, Andrew D.
Copyright Year	1989
Abstract	Solutions of silver perchlorate in methanol, ethanol, ethane-1,2-diol, isopropyl alcohol, allyl and propargyl alcohols have been exposed to 60Co γ-rays at 77 K and the resulting radicals studied using ESR spectroscopy. In addition to ĊH2OH solvent radicals, methanolic solutions gave AgII centres and a number of discrete Ag° species. The latter exhibited a range of hyperfine couplings, reflecting various degrees of solvation. Their relative yields were shown to vary according to initial AgI concentration and with added sodium perchlorate. After annealing to ca. 120 K, Ag° gave way to the molecular cluster cations Ag+2, Ag2+3, Ag3+4 and Ag4+5, previously identified by ESR and optical spectroscopy in a range of systems and shown to be formed by the sequential addition of AgI ions. Ag4+5 formation was favoured either by high initial AgI or high counterion (nitrate or perchlorate) concentration. During the silver aggregation process the solvent radicals (CH2OH) decayed and the adduct [Ag . CH2OH]+ was formed [Aiso(Ag)= 128 G]. On annealing to the softening point of the matrix these species were lost. No higher-nuclearity molecular centres were detected. However, a weak singlet in the free-spin region grew in. This is tentatively assigned to conduction electron spin resonance (CESR) in pseudo-metallic, Ag0n particles. On further melting the Ag0n signal disappeared and the sample became black, indicating the eventual formation of colloidal silver. Similar reactions were observed in ethanol, ethane-1,2-diol and isopropyl alcohol.The allyl alcohol system did not give any clearly defined Ag° centres, only solvent radicals being observed at 77K. Two possible silver–solvent adducts were detected after annealing, one with a larger Aiso(Ag) value than expected (ca. 360 G). Results for propargyl alcohol were similar, except that only one silver–solvent species was formed. Possible structures for these centres are discussed. When both systems were annealed to the matrix softening point, the adduct signals decayed and an isotropic singlet in the free-spin region was revealed. This signal was particularly strong in the propargyl system. The g value and linewidth are similar to values recently reported for CESR signals from Ag0n latent-image particles formed in silver halide matrices by photolysis.
Starting Page	3973
Ending Page	3985
Page Count	13
File Format	PDF
ISSN	03009599
Volume Number	85
Issue Number	12
Journal	Journal of the Chemical Society, Faraday Transactions 1
DOI	10.1039/F19898503973
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Allyl group Alcohol Spectral line Isotropy Valence and conduction bands Allyl alcohol Propyl group Sodium perchlorate Solvent Counterion Adduct Silver perchlorate Methanol Propargyl Spectroscopy Perchlorate Diol ESR Photodissociation Cobalt-60 Isopropyl alcohol Hyperfine structure Halide Solvation Nitrate Medical uses of silver Electron paramagnetic resonance Nucleic acid thermodynamics
Content Type	Text
Resource Type	Article
Subject	Chemistry

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Reactions of AgI ions in alcohols after radiolysis at 77 K

Reactions of Ag^I ions in alcohols after radiolysis at 77 K