Organotetrelchalkogenidcluster als funktionelle Materialien im Tintenstrahldruck und als Reaktanden gegenüber Übergangsmetallkomplexen
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Philipps-Universität Marburg
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In the framework of this dissertation, the sub-projects described in chapter “2.Zielsetzung und Motivation” were examined. The findings are summarized in figure 22 and figure 23. The first sub-project dealt with the printing of organotin sulfide clusters with adamantane topology. For this purpose, the properties of already known clusters were first examined and it was found that the solubility in organic solvents is too low to realize a significant material application by inkjet printing. For this purpose, cluster derivatives with various organic substituents were tested with regard to their solubility in organic solvents. The cluster [(p-nPentyl-PhSn)4S6] was examined regarding its non-linear optical properties, chemical and temperature stability, solubility behavior, rheological properties and surface tension in solutions and was found to be suitable for inkjet printing. The synthesis of this new white light emitter was then scaled up to a multigram scale and various ink compositions were tested in different inkjet printers. The solvent anisole turned out to be the most suitable base and an ink produced with this base was used to deposit homogeneously arranged dots on glass, which then were characterized by surface analysis. No decomposition of [(p-nPentyl-PhSn)4S6] was observed during the printing process and Raman spectra were recorded to prove that the deposited material is identical to the pure cluster. In the next step, the strings of the project’s acronyms "MOSLA" and "3DMM2O" were converted into a binary code, where "0" and "1" correspond to a blank and the [(p-nPentyl-PhSn)4S6] cluster. This binary sequence could be successfully printed on glass, which represents the "writing process" of a data storage medium. The "readout process", the measurement of WLG, was carried out in cooperation with the Rosemann group and could not be successfully realized due to a measurement setup for small sample quantities which is still in development. In general, it could be shown that organotetrelchalcogenide clusters are suitable for deposition to substrates using inkjet printing, which opens the way to further applications.
The second part of the dissertation dealt with studies on the synthesis of ternary organosiliconsulfide clusters. These compounds are interesting as potential building blocks and single-molecule precursors of complex ternary chalcogenides. For this the reactivity of [(PhSi)4S6] towards copper(I) chloride or silver(I) chloride in the presence and absence of a sulfide source was studied. In addition, the phosphine ligands PMe3, PEt3, PPh3, PMe2Ph or dppb (1,4-diphenylphosphinobutane), for the complexation of coinage metal-cations were added (see Figure 23).
In reactions with coinage metal complexes in the absence of a sulfide source, the [(PhSi)4S6]-clustercore was attacked and a {PhSi}-unit was cleaved off. Three coinage metal phosphine units were attached to the resulting {(PhSi)3S6}3− fragment, thus compensating for the negative charges. In this way, the two clusters [{(dppbCu2)CuP(Ph2)(CH2CH2)(PhSi)3S6}2] and [(Et3PAg)3(PhSi)3S6] could be synthesized. Furthermore, a reaction mechanism was postulated for the formation of [(Et3PAg)3(PhSi)3S6], according to which the formation of the cluster occurred stepwise and was only completed during crystallization. These assumptions were supported by 29Si-NMR spectroscopy. If Na2S was added to [(PhSi)4S6] in the first reaction step and then coinage metal complexes were added, similar observations could be made. In reactions of this type, a {PhSi}-unit was also cleaved off, but in contrast to the previously mentioned clusters, the negative charges were compensated by a coinage metal phosphine unit and two Na+ ions. The presence of the Na+ ions also resulted in the formation of extended coordination polymer networks. [Na2(thf)2.33][(Me3PCu)(PhSi)3S6] formed a hexameric ring system in which each hexamer additionally is linked to two other hexamers and formed a one-dimensional strand. The compound [Na2(thf)1.5][(Me2PhPAg)(PhSi)3S6] was synthesized in the same way and also formed hexameric coordination oligomers. In addition, these coordination hexamers linked again with additional rings but in this case they form a two-dimensional network.
In reactions in DCM instead of THF, the compound [(Ph3P)3Ag(μ-S)SiCl2Ph] was formed with the sterically demanding ligand PPh3 and AgCl. Further similar reactions with CuCl and the bidentate ligand dppb showed that a {CH2}-unit is transferred from decomposed solvent during the reaction and leads to the formation of [{PhCl(S)SiSCH2P(Ph2)CH2CH2}2]. In summary, it could be shown that ternary organosiliconsulfide clusters can act as building blocks for one- and two-dimensional coordination polymers. With the results described above, this dissertation contributed to the expansion of knowledge in the field of functional organotetrel chalcogenide clusters. Building on this, future work can take the next steps towards printable data storage and cluster-based three-dimensional networks.
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Created: 2024Issued: 2025-09-15Updated: 2025-09-15
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Fachbereich Chemie
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Philipps-Universität Marburg
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ger
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DoctoralThesis
DFG-subjects
Anorganische ChemieClusterÜbergangsmetallkomplexeOrganometallTintenstrahldruckHeteroadamantan
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540
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Nier, Simon: Organotetrelchalkogenidcluster als funktionelle Materialien im Tintenstrahldruck und als Reaktanden gegenüber Übergangsmetallkomplexen. : Philipps-Universität Marburg 2025-09-15. DOI: https://doi.org/10.17192/z2025.0072.