Dissertation committee:
Αθανάσιος Φιλιππόπουλος, Επίκουρος Καθηγητής, Τμήμα Χημείας, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών
Βικτωρία Μαγκριώτη, Αναπληρώτρια Καθηγήτρια, Τμήμα Χημείας, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών
Πολύκαρπος Φαλάρας, Ερευνητής Α΄, Ινστιτούτο Νανοεπιστήμης και Νανοτεχνολογίας, ΕΚΕΦΕ Δημόκριτος
Χριστίνα-Άννα Μητσοπούλου, Καθηγήτρια, Τμήμα Χημείας, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών
Ανδρέας Δανόπουλος, Καθηγητής, Τμήμα Χημείας, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών
Παναγιώτης Κυρίτσης, Καθηγητής, Τμήμα Χημείας, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών
Πατρίνα Παρασκευοπούλου, Αναπληρώτρια Καθηγήτρια, Τμήμα Χημείας, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών
Summary:
This PhD thesis has taken place in the laboratory of Inorganic Chemistry in the Dept. of Chemistry, NKUA, under the supervision of Ass. Prof. A. I. Philippopoulos. The thesis is dealing with the design of new organic ligands based on the category of 2–(2΄–pyridyl)–quinolines and subsequently the synthesis of new homoleptic Cu(I) complexes. The synthesis of the complexes took place under inert conditions (Schlenk techniques) to protect the metal center from oxidation. The reaction is based on the replacement of the coordinated MeCN from the starting material [Cu(NCMe)4](PF6) by two moles of each organic ligand. The homoleptic compounds were isolated in high yields and fully characterized by spectrocspic techniques and X–ray crystallography, when this was possible.
Also, heteroleptic complexes of the monovalent copper with two different diimine ligands were prepared. One ligand was modified to carry an ester group, while another a–diimine molecule was used as ancillary ligand. The aim of the preparation of these complexes was to develop a protocol for their synthesis. This protocol can be further applied to new heteroleptic compounds with ligands which bear carboxylic acid moieties, so as to be used as dyes in DSSC. The heteroleptic complexes were isolated in satisfactory yields and were analyticaly pure without the use of difficult and time–consuming separation techniques.
The homoleptic compounds were studied for their ability to chemisorb in the surface of titania. The complexes with carboxylic acid groups in their periphery were able to sensitize TiO2. This was further proved by FT–IR absorption and UV/Vis reflectance techniques. Compound’s (1) photoelectrochemical characteristics were studied and it showed satisfactory energy conversion, η(1)= 1.20 %, which was relatively higher than the standard (13) used for comparison (η(13)= 1.05 %).
Keywords:
Ligand design, synthesis of complexes, homoleptic Cu(I) complexes, heteroleptic Cu(I) complexes, dye sensitized solar cells.
