Synthesis and Characterization of Palladium-Containing Polyoxometalates and Polyoxometalate-Based Extended Networks

  • Polyoxometalates (POMs) are a class of discrete, anionic and soluble polynuclear metal oxides, which are generally constructed through the connectivity between early d-block metal ions and oxo linkers. The class of polyoxopalladates(II) (POPs) as a new member of POMs were discovered in 2008. In the last 14 years, around 80 POPs of various shapes, sizes and compositions have been prepared and various properties studied, with a focus on catalysis. The focus of this thesis lies in the discovery of novel POPs and their structural as well as catalytic characterization. Chapter 1 is an introduction of POMs and metal-organic frameworks (MOFs) including the history, structural properties, analytical techniques, properties and applications. In Chapter 2, the class of POPs and polyoxometalate-based metal organic frameworks (POM-MOFs) are presented. Chapter 3 represents the information on the instruments used for the characterization. In Chapter 4, the discovery of the large, neutral 40-palladium(II)-oxo cluster (POC) is presented and their solid state and solution characterization. In Chapter 5, tetranuclear and hexanuclear Pd-oxo units are discovered in the vanado- and chromo(V) capped-4-palladates(II), one dimeric 4-palladium-oxo cluster and a 4-Mn4(IV)O4-capped-6-palladate(II) as well as 10-vanado-14-palladate(II) were isolated and structurally characterized. Their catalytic semi-hydrogenation of 1-octyne and phenylacetylene was investigated as supported catalysts. In Chapter 6 Pd(IV)-containing POP and POM compounds were synthesized, which represents the first mix-valence POP and the tungsten analogue of the known molybdenum specie. In the second part of the work, the (4-triazole-phenyl)- arsonic acid functionalized POM like inverted-Keggin and hexamolybdates and their trasition-metals mediated extended network are discussed in Chapter 7 and Chapter 8 respectively.

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Publishing Institution:IRC-Library, Information Resource Center der Jacobs University Bremen
Granting Institution:Jacobs Univ.
Author:Xiang Ma
Referee:Nikolai Kuhnert, Bassem S. Bassil, Hans-Joachim Breunig
Advisor:Ulrich Kortz
Persistent Identifier (URN):urn:nbn:de:gbv:579-opus-1011125
Document Type:PhD Thesis
Date of Successful Oral Defense:2022/03/06
Date of First Publication:2022/09/21
Academic Department:Life Sciences & Chemistry
PhD Degree:Chemistry
Focus Area:Health
Call No:2022/14

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