| We used the now proven molten alkali polychalcogenide flux method to synthesize new quaternary chalcoantimonate and thiophosphate materials. The chalcoantimonate and thiophosphate fluxes are formed by the in situ fusion of A$sb2$Q/Sb/Q (A = alkali metal; Q = S, Se) or A$sb2$S/P$sb2$S$sb5$/S (A = alkali metal) forming highly reactive (Sb$sb{rm x}$Q$sb{rm y}rbracksp{rm n-}$ and (P$sb{rm x}$S$sb{rm y}rbracksp{rm n-}$ units solubilized in the excess polychalcogenide flux. These molecular building blocks coordinate to metal ions in a multitude of ways, building extended lattices stabilized by alkali cations. By examining the coordination chemistry of these systems, we discovered that the thiophosphate system is best thought of as completely different than the corresponding selenophosphate systems and different materials are formed under similar experimental conditions. In the thiophosphate system the P$sp{5+}$ species appears to be stable under a variety of conditions, and increasing the binary P$sb2$S$sb5$ concentration stabilized higher nuclearity (P$sb{rm x}$S$sb{rm y}rbracksp{rm n-}$ units. While the Sb$sp{5+}$ species is readily observed in the chalcoantimonate systems, it is exclusively observed as the discrete tetrahedral unit. The enhanced stability of the Sb$sp{3+}$ species increases the diversity of the coordination chemistry displayed by the chalcoantimonate system due to the complicated equilibrium stabilizing higher nuclearity (Sb$sb{rm x}$S$sb{rm y}rbracksp{rm n-}$ units. Changing the Lewis basicity in of the chalcoantimonate fluxes resulted in the stabilization of recognizable (Sb$sb{rm x}$S$sb{rm y}rbracksp{rm n-}$ structural fragments that could be used as building blocks forming compounds with several potential applications. Several new (P$sb{rm x}$S$sb{rm y}rbracksp{rm n-}$ and (Sb$sb{rm x}$Q$sb{rm y}rbracksp{rm n-}$ units have been synthesized and their coordination chemistry examined.;In this dissertation, the synthesis, and characterization and properties of several new silver chalcoantimonates A$sb2$AgSbS$sb4$ (A = K, Rb, Cs), Cs$sb3$Ag$sb2$Sb$sb3$Q$sb8$ (Q = S, Se), $alpha,beta$-RbAg$sb2$SbS$sb4$, and three new silver-rich gold thioantimonate compounds $alpha,beta$-Rb$sb2$Ag$sb{20}$Sb$sb4$S$sb{19}$ and Cs$sb2$Ag$sb{20}$Sb$sb4$S$sb{19}$ will be discussed. Extending this methodology to gold, three new compounds, A$sb2$AuSbS$sb4$ (A = Rb, Cs) and Rb$sb2$Au$sb6$Sb$sb4$S$sb{10}$ were synthesized, further proving the generality of the method at accommodate a variety of metals. Utilizing the corresponding thiophosphate flux a number of new quaternary compounds A$sb2$CuP$sb3$S$sb9$ (A = K, Rb, Cs), K$sb3$CuP$sb2$S$sb7$, Cs$sb2$Cu$sb2$P$sb2$S$sb6$, A$sb2$AuPS$sb4$ (A = K, Rb, Cs), and AAuP$sb2$S$sb7$ (A = Rb, Cs), were discovered. The synthetic work performed here provides the ground work for systematic synthesis, and further exploration into these and other systems. |
