Synthesis and characterization of new organic, inorganic, and organometallic tetrathiafulvalenes and cadmium selenide hybrid materials

A variety of new organic, inorganic, and organometallic complexes based on the tetrathiafulvalene (TTF) backbone have been synthesized and characterized for the development of new materials. The organic research of this thesis outlines a novel one-pot synthetic procedure and new purification route for the selective recovery of unsymmetrical TTFs. The advancements regarding this chemistry center around the phosphorus mediated coupling of two different thione heterocycles, and are based on the results of mechanistic studies using {dollar}sp{lcub}31{rcub}{dollar}P NMR. In addition to this, the successful synthesis and characterization of three new classes of tetrathiafulvalenes is presented. These materials may be used for conductive liquid crystals, metal-ion sensor, or high-spin organic materials.; The inorganic chemistry developed in this manuscript presents two firsts in TTF chemistry. The work begins with a synopsis of a new procedure for the selective generation and isolation of tetrathiafulvalene tetrathiolate (TTFS{dollar}sb4sp{lcub}4-{rcub});{dollar} and following the discovery of this ligand synthesis, we succeeded in making the first reported homobimetallic TTFS{dollar}sb4{dollar} inorganic coordination complexes using the late transition metals Pt and Ni. The reactions to produce these complexes were accomplished by introducing TTFS{dollar}sb4sp{lcub}4-{rcub}{dollar} Li{dollar}sp+{dollar}4 to the metal cis-dichlorides {dollar}rm Clsb2Pt(PPhsb3)sb2{dollar}, Cl{dollar}sb2{dollar}Ni(DPPP), and {dollar}rm Clsb2Ni(4,4spprime{dollar}-Mebipy) and subsequently isolating the products. These studies led to the recovery and characterization of first metal-TTF hybrid materials.; As a direct consequence of the difficulties encountered with the late transition metal coordination complexes, we also synthesized the first early transition metal organometallic TTFS{dollar}sb4{dollar} species using the reaction of TTFS{dollar}sb4sp{lcub}4-{rcub}{dollar} Li{dollar}sp+sb4{dollar} with {dollar}rm Clsb2TiRsb2{dollar} (R = Cp, Cp*, i-PrCp). An important result of this research was the first single crystal X-ray structure of a homobimetallic TTFS{dollar}sb4{dollar} complex. In addition to this, these materials proved useful in elucidating the photophysical and electrochemical perturbations resulting from changes in the ligand environment for a given metal. A final application of this class of compounds is that {dollar}rm Cpsb2TiTTFSsb4TiCpsb2{dollar} allows for the divergent approach (via transmetallation) to hetero- and homobimetallic coordination complexes.; As an extension of the work on early transition metal metallocenes we also attempted to make {dollar}rm Cpsb2VTTFSsb4VCpsb2{dollar} complexes in order to study the electronic spin interactions through the TTFS{dollar}sb4{dollar} bridge. However, it was subsequently discovered that the reaction chemistry, on going from Ti to V, was quite different. This led us to explore the synthesis of alkyl substituted vanadocenes to facilitate the recovery of these metal-TTF materials. A major drawback toward accomplishing this goal was the paucity of literature results concerning vanadocene dichlorides. We therefore developed a new, completely general, approach to V based metallocenes, and crystallographically characterized two new complexes.; A final area of research presented in this thesis concerns work undertaken on semiconducting CdSe nanocrystallites, or quantum dots. We developed the first nanocrystallite networks by bridging the CdSe clusters with TTFS{dollar}sb4{dollar}, and subsequently explored the resulting materials photophysical properties. In addition to this we extended the current state of knowledge and postulated a new bonding model concerned with their (CdSe) surfaces using {dollar}sp1{dollar}H NMR. This allowed us to quantify the amount of coverage and what modes of bonding are present, and relate these attributes to the photochemical propertie...