Electron Transfer in a Series of Mixed-Valence Copper(ii)-Copper(i) Complexes (Epr, Electrochemistry, It Bands, Magnetism)
Long, Russell C.
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https://hdl.handle.net/2142/70302
Description
Title
Electron Transfer in a Series of Mixed-Valence Copper(ii)-Copper(i) Complexes (Epr, Electrochemistry, It Bands, Magnetism)
Author(s)
Long, Russell C.
Issue Date
1985
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
Abstract
Three series of mixed-valence copper(II)-copper(I) complexes of macrocyclic ligands have been prepared to examine systematically the factors affecting intramolecular electron transfer. The mixed-valence complexes are similar to the one prepared by Gagne et. al. (J. Amer. Chem. Soc., 1979, 109, 4571), except that the methyl groups on the phenolic residues have been replaced by tert-butyl
substituents. The diimine linkages were also varied in the series of complexes.
(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)
The five complexes in the first series possess equivalent copper sites, where B = B' = propylene(I), 2,2'-dimethylpropylene(II), butylene(III), 2,2'-biphenylene(IV), 1,3-cyclohexylene(IX). The four complexes of the second group contain asymmetric copper sties, where B = propylene; B' = 2,2'-dimethylpropylene(V), 2,2'-biphenylene(VI), butylene(VII), 1,8-naphthalene(X). The three complexes of the third series contain electronic donor type groups, two alcohol complexes where B = B' = 2-hydroxypropylene(VIII), B = propylene; B' = 2-hydroxypropylene(XI), and complex(XII) where the diimine linkages of complex III have been chemically reduced to amine linkages. The complexes were prepared by reducing the parent dicopper(II) complexes with dithionite. Variable-temperature EPR data, taken for acetone solutions from 373 to 100 K, are presented. In the low-temperature glass medium, each complex exhibits an EPR localized spectrum. At ambient temperatures in solution, complexes I, II, III, V, VIII and XI are EPR delocalized, while complexes IV, VI, VII, IX, X and XII are EPR localized. The approximate temperature for the conversion in solution from EPR delocalized to EPR localized were gathered for the complexes delocalized at ambient temperatures. Electrochemical data, cyclic voltammograms and differential pulse voltammograms, and electronic absorption spectra, intervalence transfer (IT) bands and d-d bands are given for each complex. Magnetic data are reported for several of the dicopper(II) complexes.
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