This dissertation focuses on the synthetic exploratory synthesis of molybdenum chalcogenides and rare earth metal-rich ternary tellurides as a part of an effort to produce molecular building blocks of molybdenum chalcogenide clusters and to explore their structural relationships with solid state cluster networks. The tightly cross-linked Mo3nSe3n+2(n = 2, 3, ...∞) clusters and chain compounds react with alkali metal cyanide or cyanide salt mixtures at temperatures of 450-675 °C to yield reduced, cyanide-terminated molybdenum chalcogenide clusters that are thermodynamically stable. At temperatures of 650-675 °C, linear chain compounds I6[Mo6Se8(CN)4(CN)2/2] (MI = K, Cs) were prepared from reactions of Mo6Se8 or elemental starting materials, Mo and Se with excess molten cyanide (KCN, CsCN). These are the first known compounds to feature linking of Mo6Se8 clusters via cyanide bridges. Magnetic susceptibility and EPR measurements indicate that there is one unpaired electron per cluster. A new reduced molecular octahedral complex, Na8[Mo6Se8(CN)6]•20H2O was prepared by the reduction of [Mo6Se8(CN)6]7-with Zn in an aqueous NaCN solution. Single crystal structure was determined. Cyclic voltammetric measurements in basic aqueous media show multiple reversible redox waves corresponding to [Mo6Se8(CN)6]6-/7-, [Mo6Se8(CN)6]7-/8-, [Mo6Se8(CN)6]8-/9-redox couples with half-wave potentials of E1/2 = -0.442 V, -0.876 V, and 11.369 V respectively versus the standard hydrogen electrode (SHE). UV-Vis studies support the presence of the reduced cluster compound. New reduced molecular tetrahedral complexes, K7Na[Mo4Se4(CN)12]•5H2O•MeOH, Na4Cs7[Mo4Se4(CN)12]Cl3, Na8[Mo4Se4(CN)12], and Na4K4[Mo4Se4(CN)12]•12H2O were prepared. Preparation of Na8[Mo4Se4(CN)12] is an improved method for the synthesis of the Mo4Se4 core. Half-wave potentials of E1/2 for the [Mo4Se4(CN)12]6-/7-and [Mo4Se4(CN)12]7-/8-couples are 0.233 V, and -0.422 V respectively versus SHE. The molecular cubane clusters [Mo4Se4(CN)12]7-/8-play an essential role in the process by which the discrete [Mo6Se8(CN)6]6-and [Mo6Se8(CN)6]are excised from the CN-linked chain compound, K6Mo6Se8(CN)5. A new rare-earth telluride compound with the empirical composition of Gd4NiTe2 was synthesized from a high-temperature solid-state reaction. Gd4MTe2 (M = Ni) crystallizes in the orthorhombic space group Pnma. This unprecedented structure consists of a cluster condensation of Ni-centered gadolinium tricapped trigonal prisms along the rectangular faces of the trigonal prism such that the Ni atoms act as two of the caps to the trigonal prisms.
| Identifer | oai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/348 |
| Date | 30 September 2004 |
| Creators | Magliocchi, Carmela Luisa |
| Contributors | Hughbanks, Timothy R. |
| Publisher | Texas A&M University |
| Source Sets | Texas A and M University |
| Language | en_US |
| Detected Language | English |
| Type | Book, Thesis, Electronic Dissertation, text |
| Format | 4058139 bytes, 204065 bytes, electronic, application/pdf, text/plain, born digital |
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