Sinteza i supramolekulske interakcije polinorbornanskih bis-porfirina

doctoral thesis

• Title (english): Synthesis and supramolecular interactions of polynorbonane bis-porphyrins
• Author: Anamarija Briš
• Mentor: Davor Margetić (mentor)
• Committee member: Srđanka Tomić-Pisarović (predsjednik povjerenstva)
• Committee member: Davor Margetić (član povjerenstva)
• Committee member: Leo Frkanec (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2015-04-28, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

U sklopu disertacije sintetiziran je novi bis-porfirin, tzv. "molekulska pinceta", koja uslijed slabih nekovalentnih interakcija djeluje kao molekulski receptor za niz organskih supstrata. "Molekulska pinceta" se sastoji od krutog mosta na bazi norbornanskih jedinica koji povezuje porfirinske prstenove metalirane s cinkom. Sinteza novih spojeva uključuje optimiranje postojećih sintetskih metoda te korištenje ekološki prihvatljivijih postupaka kao što su upotreba mikrovalnog reaktora i kugličnog mlina. UV-Vis spektroskopijom je određena selektivnost i jačina nekovalentnih interakcija bis-porfirina i raznih cikličkih i acikličkih diamina. Cink unutar metaloporfirina "molekulske pincete" aksijalno koordinira diaminske supstrate, dajući 1:1 kompleks s visokim konstantama stabilnosti. Bis-porfirin također čini stabilan kompleks s bispiridinskim derivatom fulerena C60 i pri tome ima visoku konstantu. Računski je pokazano da se HOMO i HOMO-1 orbitale nalaze na porfirinskim jedinicama, dok je LUMO na fulerenu što ukazuje na ponašanje porfirinskih jedinica kao donora, a fulerena kao akceptora elektrona u donor-akceptorskim sustavima sposobnim na fotoinducirani prijenos elektrona dajući vrste s razdvojenim nabojem.

Abstract (english)

Within the scope of the thesis new bis-porphyrin called "molecular tweezers" has been synthesised, which due to the weak noncovalent interactions acts as a molecular receptor for a variety of organic substrates. "Molecular tweezers" consists of a rigid norbornane bridge that connects porphyrin rings metalated with zinc. Synthesis of novel compounds includes the optimization of existing synthetic methods and the use of environmentally more friendly methodologies such as the use of microwave reactors and ball mill. The selectivity and strength of noncovalent interactions of bis-porphyrin and various cyclic and acyclic diamines have been determined by UV-Vis spectroscopy. Zinc within metalloporphyrins of bis-porphyrin receptor axially coordinates diamine substrates giving sandwich complexes with large association constants. Bis-porphyrin also makes stable complex with bispyridine functionalized fullerene C60 with large association constant. Computationally has been shown that HOMO and HOMO-1 orbitals are located on porphyrin units while LUMO is positioned on fullerene suggesting porphyrins as electron donors and fullerene as electron acceptor in donor-acceptor system capable of photoinduced electron transfer generating charge-separated species.

• Keywords: bis-porfirini; diamini; fotoinducirani prijenos elektrona; fuleren C60; metaloporfirini; supramolekulske interakcije
• Keywords (english): bis-porphyrins; diamine; photoinduced electron transfer; fullerene C60; metalloporphyrins; supramolecular interactions
• Language: croatian
• URN:NBN: urn:nbn:hr:217:333350
• Study programme: Title: Doctoral study in chemistry; Study programme type: university; Study level: postgraduate; Academic / professional title: doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija (doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija)
• Type of resource: Text
• Extent: 146 str. ; 30 cm
• File origin: Born digital
• Access conditions: Closed access
• Created on: 2018-09-06 08:28:19