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Identifier

000398686

Title

Συνθετική και δομική χαρτογράφηση ανόργανων-οργανικών υβριδικών υλικών και μελέτη των ιδιοτήτων τους

Alternative Title

Synthetic and stuctural mapping of inorganic-organic hybrid materials and study of their properties

Author

Αναγνώστου, Ζαφειρία Α.

Thesis advisor

Δημάδης, Κωνσταντίνος

Reviewer

Κουτσολέλος, Αθανάσιος
Σαββάκης, Κωνσταντίνος
Τρικαλίτης, Παντελής
Μήλιος, Κωνσταντίνος
Κατερινόπουλος, Χαράλαμπος
Σπύρος, Απόστολος

Abstract

This Τhesis is focused on three main axes: (a) The synthesis of hybrid inorganic-organic materials based on backbones that consist of divalent metal ions, (poly)phosphonate ligands and a polypyridyl-like co-ligand. (b) The structural and the spectroscopic characterization of the synthesized materials and (c) The preliminary study of some of their properties. This Thesis explores the rich properties of phosphonic acids for the construction of inorganic-organic hybrid materials, the structure of which is based on metal phosphonate frameworks, but also incorporates a second polypyridyl-like ligand (co-ligand). The ultimate goal of this research was the systematic discovery and documentation of a large number of such materials that posses a plethora of structural architectures and properties. Their structural variability depends on the nature of the co-ligand and is expected to impart important influence to their properties. Hence, the following components were utilized in the synthetic systems: (a) Mono- and di-phosphonate ligands, as well as carboxyphosphonate and hydroxy-phosphonate ligands, such as phenylphosphonic acid (PPA), ethane-diphosphonic acid (EDPA), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 3-phosphonopropionic acid (CEPA), και phosphonoacetic acid (PAA). (b) Divalent metal ions: Cu²⁺, Ni²⁺, Mn²⁺, Co²⁺ και Zn²⁺. (c) Co-ligands, such as the chelating 2,2’-bipyridine, and 1,10-phenanthroline, and the bridging 4,4’-bpy. The results of this Thesis state the following: (a) Chelating N-heterocyclic ligands can be incorporated in synthetic procedures that involve a metal ion and a phosphonate and can dramatically influence the outcome of the synthesis, regarding the structure and dimensionality of the final product. Hence, in a way, the co-ligand directs the synthesis to novel products with new structures and topologies. (b) All the co-ligands used, either chelating (2,2′-bpy, phen) or bridging (4,4’-bpy), are found coordinated to the metal centers (Cu²⁺, Ni²⁺, Zn²⁺, Co²⁺, Mn²⁺), in the presence of various phosphonic acids (HEDP, PPA, PAA, CEPA and EDPA), yieding either ionic complexes or 1D, 2D, or 3D coordination polymers. (c) The phosphonate can sometimes play the role of the counterion, while it remains non-coordinated, eg. in the material [Ni(4,4’-bpy)(EDPA)(H₂O)₄]•H₂O. (d) The metal coordination geometry is dependent on the type of phosphonate ligand used. Therefore, a variation in coordination number has been observed. (e) Crucial factors that influence the structure of the final product are the π-π interactions between aromatic moieties of the polypyridyl co-ligands, and the extensive hydrogen-bonded networks.

Language

Greek

Subject

(poly)phosphonates

Bipyridine

Hybrid materials

Metal organic frameworks

Metal phosphonates

Phosphonic acid

Διπυριδίνη

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