Struktura i samoudruživanje aromatskih dinitrozo spojeva

doctoral thesis

• Title (english): Structure and self-assembly of aromatic dinitroso compounds
• Author: Petar Bibulić
• Mentor: Hrvoj Vančik (mentor)
• Mentor: Ivana Biljan (komentor)
• Committee member: Vladislav Tomišić (predsjednik povjerenstva)
• Committee member: Olga Kronja (član povjerenstva)
• Committee member: Predrag Novak (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2018-11-23, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

Aromatski C-nitrozo spojevi s dvije i više nitrozo skupina zanimljiva su građevna jedinica u
supramolekulskoj kemiji zbog svojstva povezivanja u azodiokside, a na stvaranje azodioksidne
veze moguće je utjecati UV zračenjem i temperaturom. Priređeni su novi aromatski dinitrozo
spojevi s različitim premosnicama između aromatskih prstena te je ispitan utjecaj strukture
premosnice na samoudruživanje i reaktivnost u otopini, čvrstom stanju i na modificiranoj
površini zlata (111). Radi boljeg razumijevanja mehanizma reakcije nastajanja azodioksida u
čvrstom stanju provedena su izotermna i neizotermna kinetička mjerenja. Izotermni
eksperimentalni podatci obrađeni su nelinearnom regresijom prema empirijskim i
mehanističkim modelima, dok su neizotermna mjerenja analizirana često korištenim
izokonverzijskim metodama. Nastajanje azodioksida u otopini praćeno je spektroskopijom
NMR na više temperatura, dok je udruživanje na uređenim površinama zlata praćeno
elipsometrijom. Rezultati upućuju da se na slobodne nitrozo skupine na zlatu veže nekoliko
podjedinica aromatskih dinitrozo derivata, dok u otopini nastaju uglavnom dimerne vrste.

Abstract (english)

Aromatic C-nitroso compounds with more than one nitroso groups are interesting
supramolecular building blocks due to their property to self-assemble into UV- and
thermo-active azodioxy molecular structures. Several new aromatic dinitroso compounds with
different spacers between the aromatic rings were prepared. Relation between the spacer
structure, self-assembly and reactivity of dinitroso compounds in the solid state, solution and
on modified, planar gold (111) surface was examined. Isothermal and non-isothermal
solid-state kinetic measurements were performed to analyze reaction mechanisms.
Experimental data were analyzed by both semiempirical and reaction-mechanism based
model-fitting methods, as well as by common isoconversional procedures. Azodioxide
formation in solution was investigated by variable-temperature NMR spectroscopy, while
monomer association on the modified gold surface was monitored by ellipsometry. The
observed processes indicated that dimer formation was prevalent in the solution, while layers
on gold surface consisted of up to several monomeric subunits.

• Keywords: čvrsto stanje; kinetika; nitrozo; kemijska ravnoteža; samoudruživanje Mentori: dr.
• Keywords (english): nitroso-azodioxidesolid-state reactions; kinetics; chemical equilibrium; self-assembly
• Language: croatian
• URN:NBN: urn:nbn:hr:217:180450
• 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: 165 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2019-11-27
• Created on: 2019-01-08 10:50:49