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PHOTOPHYSICS OF DIOXORHENIUM(V) IN NAFION *
Author(s) -
Thorp H. Holden,
Gray Harry B.
Publication year - 1991
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1991.tb02063.x
Subject(s) - nafion , aqueous solution , excited state , chemistry , solvent , ion , ethylene glycol , membrane , electrochemistry , polymer , absorption (acoustics) , metal , metal ions in aqueous solution , analytical chemistry (journal) , photochemistry , materials science , organic chemistry , electrode , atomic physics , physics , biochemistry , composite material
The emission properties of [ReO 2 (py) 4 ] + in Nafion perfluorosulfonated membranes have been investigated. The excited state of [ReO 2 (py) 4 ] + is a sensitive probe of microheterogeneous environments in aqueous solution (Thorp el al. (1989) J. Am. Chem. SOC. 111 ,4364–4368). The absorption and emission maxima indicate that the interior of the membrane is quite polar, similar to ethylene glycol (Z‐85). Two well‐resolved emission components show different lifetimes (τ 1 (H 2 O) = 250 ns, τ 2 ,(H20) = 1.3 μs) and isotope effects (3.0, 2.4), indicative of varying degrees of solvent accessibility. The evidence suggests that [ReO 2 (py) 4 ] + occupies two distinct regions in the polymer film, assigned as the interfacial region and the ion‐cluster region based on previous electrochemical studies involving other metal ions.