Hybrid inorganic-organic, organic charge transfer, and radical based compounds with chalcofulvalene donors and organic acceptors

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Title: Hybrid inorganic-organic, organic charge transfer, and radical based compounds with chalcofulvalene donors and organic acceptors
Author: Reinheimer, Eric Wade
Abstract: 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 .
URI: http : / /hdl .handle .net /1969 .1 /ETD -TAMU -2452
Date: 2009-05-15

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Hybrid inorganic-organic, organic charge transfer, and radical based compounds with chalcofulvalene donors and organic acceptors. Available electronically from http : / /hdl .handle .net /1969 .1 /ETD -TAMU -2452 .

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