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Description:
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The primary focus of this dissertation is the electrochemical preparation of radical
cation salts utilizing the donor o -4 ,4’ -dimethyltetrathiafulvalene (o -Me2TTF ) and
spherical , tetrahedral , octahedral , bimetallic , cyanometallate , and polyoxometallate
anions . Other donors , such as tetramethyl (tetraselenafulvalene ) (TMTSF ) ,
tetramethyl (tetrathiafulvalene ) (TMTTF ) , bis (ethylenedithio )tetrathiafulvalene (BEDTTTF
or ET ) , and bis (propylenedithio )tetrathiafulvalene (BPDT -TTF or PT ) also found
use in the preparation of salts in the course of this study . X -ray structural
characterization of these salts revealed stacking between donor molecules containing
significant S•••S interactions in the solid state . Various salts were subjected to either
conductivity or molecular magnetism measurements in order to determine the level of
itinerant electron density and magnetic contribution from paramagnetic charge
compensating anions . In order to expand the library of TTF -containing hybrid materials
prepared through metathesis , salts of other tetrathiafulvalenium radicals have also been
prepared and characterized crystallographically and by select spectroscopic methods . In an effort to gain further information on formation of organic charge transfer
complexes , TTF was combined with nitrofluorenone family of acceptors as well as the
organocyanide acceptors HAT - (CN )6 (HAT - (CN )6 = 1 ,4 ,5 ,8 ,9 ,12 -hexaazatriphenylenehexacarbonitrile )
and TCNB (TCNB = 1 ,2 ,4 ,5 -tetracyanobenzene ) . The complexes were
characterized using X -ray crystallography , infrared spectroscopy , and molecular
magnetism . All of these techniques showed that all compounds underwent little to no
charge transfer .
Commencing in 2003 , the combined work of Dunbar and Omary revealed that
systems combining inorganic donors with chelating , sulfur -based ligands and organic
acceptors could have their spectroscopic response tuned to display low -energy charge
transfer bands extending into the near -IR making them suitable candidates as
photosensitizing dyes for semiconductors . In keeping with this idea , new layered charge
transfer compounds combining the nitrofluorenone family of acceptors and the inorganic
donor Pt (dbbpy ) (tdt ) (tdt = 3 ,4 -toluenedithiolate ) were prepared . The resulting
complexes were characterized utilizing X -ray crystallography as well as both
spectroscopic and electrochemical methods . Similar analyses were also conducted on
various platinum /terpyridine salts and illustrated a level of spectroscopic tunability to that
observed for the supramolcular systems composed of inorganic donors and organic
acceptors . |