Flux synthesis of new complex compounds uses an excess of molten metals or salts as a reaction medium. This solution-based method is a
valuable tool in materials synthesis, enabling the solid-state chemist to achieve reactivity at relatively low temperatures compared to
traditional solid-state reactions. A growing effort in the field of flux synthetic chemistry is to enable the directed synthesis of
materials. This entails being able to predict products that will form, or at least the building blocks that will be incorporated into the
products. It is therefore necessary to explore various flux systems in order to develop trends that will better help chemists understand the
mechanisms by which compounds and their building blocks form. To this end, two flux mixtures, Ca/Li and Yb/Li, were explored and several new
complex compounds were discovered which feature a range of structural and electronic properties. Calcium and ytterbium commonly form solid
solutions in compounds due to similarities in their ionic radii and valence. Calcium melts above 800°C, but the addition of lithium lowers
this melting point drastically to around 300°C. Unfortunately, there is no phase diagram for mixtures of ytterbium and lithium, so attempts
to grow new crystals in this melt was largely speculative on the basis that ytterbium may behave similarly to calcium and produce a
low-temperature solution when mixed with sufficient lithium. This is supported by the fact that ytterbium has a similar melting point to
calcium, and binary phase diagrams incorporating ytterbium or calcium mixed with other metals feature similar trends. Ca/Li flux is able to
dissolve refractory elements such as carbon, as well as salts such as Ca3N2 and CaH2. New carbide and hydride compounds formed from Yb/Li
flux suggest similar capabilities, however reactivity with nitride salts is still undetermined. Electropositive fluxes in general are useful
solvents for the growth of new complex carbides, nitrides and hydrides. Compounds containing these light elements are extremely important for
many industrial applications. Therefore, further exploration into making new complex compounds incorporating them is merited. Several new
compounds including Ca12InC13-x, Ca6Te3N2, Ca6(LixFe1-x)Te2N3, Ca8In2SiN4, Ca3SiN3H, and Yb~51In13H27 were synthesized from either Ca/Li or
Yb/Li flux mixtures. Their synthesis, structural and electronic properties, as well as potential applications are discussed
herein. / A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the
requirements for the degree of Doctor of Philosophy. / Fall Semester 2017. / November 09, 2017. / Includes bibliographical references. / Susan Latturner, Professor Directing Dissertation; Theo Siegrist, University Representative; Thomas
Albrecht-Schmitt, Committee Member; Igor V. Alabugin, Committee Member.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_605096 |
| Contributors | Dickman, Matthew J. (Matthew Jansen) (author), Latturner, Susan (professor directing dissertation), Siegrist, Theo (university representative), Albrecht-Schmitt, Thomas E. (committee member), Alabugin, Igor V. (committee member), Florida State University (degree granting institution), College of Arts and Sciences (degree granting college), Department of Chemistry and Biochemistry (degree granting departmentdgg) |
| Publisher | Florida State University |
| Source Sets | Florida State University |
| Language | English, English |
| Detected Language | English |
| Type | Text, text, doctoral thesis |
| Format | 1 online resource (146 pages), computer, application/pdf |
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