A series of new tin (IV) σ-bonded ferrocene-containing porphyrins, FcXSnTPP
complexes (X = Fc or Cl; TPP = 5,10,15,20-tetraphenylporphyrin(2-)) and FcXSnOEP
complexes (X = Fc or OEt; OEP = 5,10,15,20-octaethylporphyrin(2-)), have been
prepared and characterized using 1H NMR, UV-Vis, and MCD spectroscopy. Structures
of all target compounds were confirmed by single crystal X-ray analysis. The redox
properties of these compounds were investigated using electrochemistry,
spectroelectrochemistry, and chemical oxidation techniques. It has been found that the
presence of one or more ferrocene groups leads to controlled redox behaviors that can
have potential application in optical and fluorescent sensors. Three new indium(III) polyferrocenyl
porphyrins (XInTFcP complexes [X = Cl, OH, or Fc; TFcP = 5,10,15,20-
tetraferrocenylporphyrin(2-)] have also been prepared and investigated by the similar
methods. Through redox property analysis, mixed-valence state formations were
observed between Fe(II)-Fe(III) centers. The mixed-valence nature of these compounds
makes them candidates for molecular electronics. DFT calculations were also performed
in order to understand the electronic structure and its relation to the redox properties involved for some of the compounds
University of Minnesota M.S. thesis. July 2011. Major: Chemistry. Advisor: Dr. Victor Nemykin. 1 computer file (PDF); x, 124 pages.
Dammer, Samantha Jolene.
Synthesis and characterization of new ferrocenyl-containing Tin(IV) and Indium(III) porphyrins..
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