Electrochemical and spectroelectrochemical studies of metallocorroles and electrochemical quartz crystal microbalance studies of buckminsterfullerene films

Thesis/Dissertation · Wed Jan 01 04:00:00 EST 1992

OSTI ID:7069914

Koh, W

This dissertation consists of two major parts. In the first part, the redox properties of metallocorroles, (OMC)Rh(PPh[sub 3]), (OMC)Co(PPh[sub 3]), and (Et[sub 4]Me[sub 4]CH)Cu, where OMC is the trianion of 2,3,7,8,12,13,17,18-octamethylcorrole and Et[sub 4]Me[sub 4]CH is the dianion of 3,8,12,17-tetraethy-2,7,13,18-tetramethylcorrole, were investigated by electrochemical and spectroelectrochemical methods in nonaqueous media. The rhodium(III) and cobalt (III) corroles undergo up to three oxidations and two reductions while copper(II) corrole undergoes up to two oxidations and two reductions. The oxidations of all three compounds occur at the corrole [pi]-ring system. The reductions of Rh(III) and Co(III) corrole occur at the metal ion while the reductions of Cu(II) corrole occur at corrole macrocycle. Overall oxidation reduction mechanisms are proposed for all three complexes and they are compared with the reactions of rhodium, cobalt, and copper porphyrins under the same experimental conditions. In the second part, the electrosynthesis, electrodoping/undoping, and electrodissolution of thin films of C[sub 60] and its salts were studied in acetonitrile at a Au/quartz electrode by simultaneous electrochemical measurements and microweighing with an electrochemical quartz crystal microbalance. The films were electrodeposited either from C[sub 60][sup 3[minus]] solutions containing (TBA)ClO[sub 4], where TBA[sup +] is tetra-n-butylammonium cation, or from C[sub 60][sup 2[minus]] solutions containing CsAsF[sub 6], KPF[sub 6], or Ca(PF[sub 6])[sub 2]. The composition of C[sub 60][sup 0] films electrodeposited at a constant potential from C[sub 60][sup 3[minus]] in acetonitrile contg. (TBA)ClO[sub 4] was controlled by the initial C[sub 60][sup 3[minus]] concentration and/or the electrodeposition potential. The C[sub 60][sup 0] films were electrodoped with TBA[sup +] upon electroreduction.

• Research Organization: Houston Univ., TX (United States)
• OSTI ID: 7069914
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360601 -- Other Materials-- Preparation & Manufacture
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKALI METALS
ALKALINE EARTH METALS
CALCIUM
CARBON
CESIUM
CHEMICAL COATING
CHEMICAL REACTIONS
CHEMISTRY
COBALT COMPLEXES
COMPLEXES
COPPER COMPLEXES
DEPOSITION
DOPED MATERIALS
ELECTROCHEMICAL COATING
ELECTROCHEMISTRY
ELEMENTS
FILMS
FULLERENES
MATERIALS
METALS
NONMETALS
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POTASSIUM
REDOX REACTIONS
RHODIUM COMPLEXES
SURFACE COATING
THIN FILMS
TRANSITION ELEMENT COMPLEXES