Department of Chemistry
Library of the School of Science

2021-12-02

2021

Charalampous Eleni

Χ. Μητσοπούλου, Καθηγήτρια ΕΚΠΑ
Ε. Σημαντήρας, Ερευνητής Α’, Εθνικό Ίδρυμα Ερευνών
Κ. Μπεθάνης, Επίκουρος Καθηγητής, Γεωπονικό Πανεπιστήμιο Αθηνών
Ν. Ψαρουδάκης, Επίκουρος Καθηγητής, ΕΚΠΑ
Κ. Μεθενίτης, Αναπληρωτής Καθηγητής, ΕΚΠΑ
Σ. Κοΐνης, Αναπληρωτής Καθηγητής, ΕΚΠΑ
Α. Χρυσανθόπουλος, Επίκουρος Καθηγητής, ΕΚΠΑ

«Σύνθεση συμπλόκων ενώσεων και υλικών που προκύπτουν από τετραθειομεταλλικά διανιόντα»

Greek

«Synthesis of complexes and materials derived from tetrathiometallic ions»

The present thesis refers to the synthesis of new complexes and materials derived from tetrathiometallic dianions.
The first part of the thesis presents the synthesis and characterization of the monoanionic heterotrimetallic complexes [L2Rh(μ-S)2M(μ-S)2CuCl]- and the heteropentametallic complexes [L2Rh(μ-S)2Μ(μ-S)2Ni(μ-S)2Μ(μ-S)2RhL2] (M = Mo, W). The complex (NEt4)[(cis-dppen)Rh(μ-S)2W(μ-S)2CuCl] was characterized by X-ray diffraction analysis. The detailed DFT study of the electronic structure of the complexes [(COD)Rh(μ-S)2M(μ-S)2CuCl]¯, [(P(OMe)3)2Rh(μ-S)2M(μ-S)2CuCl]¯ and [(P(OMe)3)2Rh(μ-S)2M(μ-S)2Ni(μ-S)2M(μ-S)2Rh(P(OMe)3)2 (M = Mo, W) has revealed the existence of extended electron delocalization over the four-membered Rh(μ-S)2M(μ-S)2Cu and Rh(μ-S)2M(μ-S)2Ni(μ-S)2M(μ-S)2Rh rings and hence the possibility of electronic communication between the metal centers. The electronic spectra of the complexes with P(OMe)3 ligands were studied with TDDFT calculations and the main absorption band in the visible was assigned to ν(RhMo/W) electron transfer transition. Furthermore, interesting correlations of UV-vis and 31P NMR experimental data with the electronic parameter of Tolman (TEP) and the electronic parameters of the QALE method were found, respectively.
The second part of the thesis presents the synthesis and study of new amorphous materials. The reaction of RhCl3 3H2O and (NH4)2MoS4, in aqueous solution in a 2/3 molar ratio, results in the formation of a black solid, from which two different products were derived, depending on the way of heating at 150 οC. Heating of the black product in a laboratory drying oven, in the presence of atmospheric air, followed by application of 10 ton mechanical pressure, results in the formation of the black solid RM23SO4, while heating in vacuum results in the formation of the black solid RM23. Both products were studied with FTIR, TEM, SEM, EDX, ΗRΤΕΜ and XPS measurements. The main components of RM23SO4 seems to be a mixture of oxo(thio)-molybdenum species and rhodium sulfate and, RM23 is a mixture of molybdenum and rhodium oxides and/or sulfides. Finally, it was found that both products contain a considerable amount of carbon although no carbon containing reagent has been used, meaning that CO2 capture takes place.

Science

tetrathiomolybdate, tetrathiotungstate, rhodium, copper, nickel, UV-vis, 31Ρ NMR, DFT, QALE, composite material.

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Yes

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https://pergamos.lib.uoa.gr/uoa/dl/object/2967861