Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 3973 - 3986 (1989)
Update date:2022-08-10
Topics:
Janes, Robert
Stevens, Andrew D.
Symons, Martyn C. R.
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 .CH2OH solvent radicals, methanolic solutions gave AgII centres and a number of discrete Ag0 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, Ag0 gave way to the molecular cluster cations Ag2+, Ag32+, Ag43+ and Ag54+, previously identified by ESR and optical spectroscopy in a range of systems and shown to be formed by the sequential addition of AgI ions.Ag54+ 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 and the adduct 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.Onfurther melting the Ag0n signal disappeared and the sample became black, indicating the eventuel formationof 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 Ag0 centres, only solvent radicals being observed at 77 K.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.
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