Unit:
Τομέας ΙΙΙ [Ανόργανη Χημεία – Ανόργανη Χημική Τεχνολογία – Περιβαλλοντική Χημεία]Library of the School of Science
Author:
Κατσένης Αθανάσιος
Dissertation committee:
Ιωάννης Σ. Παπαευσταθίου Επίκουρος Καθηγητής ΕΚΠΑ (Επιβλέπων), Μητσοπούλου Χριστιάνα, Καθηγήτρια, ΕΚΠΑ , Μήλιος Κωνσταντίνος Επίκουρος Καθηγητής Παν/μιο Κρήτης
Original Title:
Ανάπτυξη Στρατηγικών Σύνθεσης, Χημική Δραστικότητα και Χαρακτηρισμός Μεταλλικών Πλειάδων και Μεταλλο?Οργανικών Κατασκευών
Translated title:
Development of Synthetic Strategies, Chemical Reactivity and Characterization of Metal Clusters and Metal-Organic Frameworks
Summary:
In the context of this thesis were synthesized new metal clusters, with
interesting magnetic properties, that can potentially be used as secondary
building units (SBUs) for the construction of polymeric complexes /
Metal-Organic Frameworks (MOFs). Following this synthetic strategy, we isolated
nine metal clusters, five of which could serve as SBUs for the construction of
MOFs, two coordination polymers that are based on single-molecule magnets and a
polymeric chain that exhibits the properties of a single-chain magnet. One of
the above mentioned metal clusters comprises 42 Mn(II) ions which is the
largest Mn(II) metal cluster. Both clusters and MOFs were characterized by
x-ray crystallography while we studied their magnetic properties and analyzed
the topological features of the MOFs.
In our efforts to develop new, cost-effective and environmentally benign
synthetic strategies for MOFs and metal clusters we exploited a new strategy
known as mechanochemistry. Based on the principles of mechanochemistry, we were
able to synthesize two new mononuclear metal complexes, three new metal
clusters and three new coordination polymers based on Zn(II).
Furthermore, we synthesized three previously known MOFs using a novel “green”
synthetic approach known as “accelerated ageing” in which there is no use of
organic solvents and simultaneously we can achieve very high yields with very
low energy cost.
Finally, with an initial aim to simplify the reported mechanosynthesis of ZIF-8
which is one of the few commercially manufactured MOFs (Basolite Z1200®), we
discovered a new metastable phase. This new phase is a three-dimensional MOF
with a hitherto unknown topology which we name katsenite (three letter code:
kat).
Keywords:
Metal-Organic Frameworks, Metal Clusters, Molecular Magnetism, Single-Molecule Magnets, Mechanochemistry
Number of index pages:
1-10
Number of references:
228
File:
File access is restricted.
document.pdf
7 MB
File access is restricted.
