Magnetic susceptibility studies over the temperature range 87-330°K, on sixteen complexes of copper (11) are reported. The compounds are conveniently divided into two groups. Group I compounds (copper (11) benzoate and its monopyridine adduct, copper (11) meta-chlorobenzoate and its monopyridine and mono-p-dioxane adducts and the monopyridine and hemipyridine adducts of copper (11) para-chlorobenzoate ) possess magnetic properties expected for a binuclear system and values of the exchange integrals have been calculated, for these compounds. The group 11 compounds (the dipyrldlne adducts and the basic salts of copper (ll) benzoate, copper (11) ortho-, meta- and para-chlorobenzoate ) exhibit only weak magnetic interaction --- their magnetic susceptibilities obeying the Curie-Weiss law with small Weiss constants --- and they are considered to have polymeric structures. Copper (11) para-chlorobenzoate exhibits properties intermediate between the group I and 11 compounds. Confirmatory evidence for assigning binuclear structures to the group I compounds has been obtained from the presence, in the spectra of the group I compounds, of a band at about 400 mμ which is absent from the spectra of the group 11 compounds. Infrared spectra are reported for all the compounds studied and a partial assignment has been made. / Science, Faculty of / Chemistry, Department of / Graduate

The electrochemistry of solid electrodes of charge transfer complexes of tetracyanoquinodimethane (TCNQ) and copper complexes with nitrogen containing chelates, such and dipyridylamine (dpaH), bipyridyl (bpy) and 1,10-dimethyl-2,9-phenanthroline (dmp), has been investigated with cyclic voltammetry. Pressed pellet electrodes of these complexes exhibit a broad electrochemically stable region. The oxidative and reductive breakdown reactions involve solid state reactions into the bulk electrode. These materials also act as electron mediators for glucose oxidation in glucose oxidase modified electrodes. The structure of the model compound, copper(I)(dpaH)₂Cl has been determined to have a distorted tetrahedral coordination sphere. The electrochemistry of solid electrodes of charge transfer complexes of tetrathiafulvalene (TTF) with copper chloride and copper bromide has been investigated with cyclic voltammetry. Pressed pellet electrodes do not exhibit a broad stable region, as do the TCNQ complexes. A preliminary structure of the organic part of tetramethyltetraselenafulvalene copper chloride has been determined from the solution of the Patterson function and exhibits a displacive modulation with a repeat unit of seven TMTSF molecules. (TTF)(SCN)₀ͺ₆₆ and (TTF)Cu(SCN)₂ have been investigated by infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. (TTF)(SCN)₀ͺ₆₆ crystallized in a tetragonal space group with a disordered column of thiocyanate anions. (TTF)Cu(SCN)₂ is an insulator with a two-dimensional network of Cu(SCN)₂⁻ ions. X-ray crystal structures of four compounds prepared in association with copper complex chemistry have been determined; (1) 5,5'-dibromo-2,2'-bithiophene, (2) 3,5,5'-tribromo-2,2'-bithiophene, (3) Cu(dmp)(CN)₂ ⁻ · Bu₄N⁺ and (4) the 1:2 adduct of dimercaptosuccinic acid and dimethylformamide.