Priprava i svojstva novih diamantoidnih etera

doctoral thesis

• Title (english): Synthesis and properties of novel diamondoid ethers
• Author: Jasna Alić Stolar
• Mentor: Marina Šekutor (mentor)
• Committee member: Vesna Petrović-Peroković (predsjednik povjerenstva)
• Committee member: Mirta Rubčić (član povjerenstva)
• Committee member: Zoran Glasovac (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2023-01-27, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

U okviru ove doktorske disertacije provedena je sinteza novih tercijarnih diamantoidnih etera
koji se sastoje od adamantanske i diamantanske podjedinice direktno povezane kisikovim
atomom. Uz klasičnu sintezu u otopini/talini, provedena je i mehanokemijska sinteza koja je
pokazala brojne prednosti u usporedbi s klasičnom sintezom. Novopripravljenim spojevima
ispitana je mogućnost samoorganizacije u 2D i 3D prostoru pri čemu su korištene tehnika
pretražne tunelirajuće mikroskopije, tehnika helijevih nanokapljica te tehnika difrakcije
rendgenskog zračenja na jediničnom kristalu. Uočeno je uređeno samoudruživanje
diamantoidnih etera pri čemu način samoorganizacije proizlazi iz početnih geometrijskih
struktura ispitivanih molekula te je proces uzrokovan prostornim međumolekulskim
interakcijama. Za dodatnu karakterizaciju nastalih površinskih slojeva korištena je računalna
analiza kojom je razjašnjen utjecaj kisikovog atoma na usmjeravanje molekula prema
površini, te je potvrđen presudan utjecaj Londonovih disperzijskih interakcija između
diamantoidnih kaveza na samoorganizaciju adsorbiranih molekula. Analiza difrakcijom
rendgenskog zračenja i diferencijalnom pretražnom kalorimetrijom potvrdila je postojanje
faznih transformacija diamantoidnih etera u čvrstom stanju.

Abstract (english)

In the scope of this thesis, new tertiary diamondoid ethers consisting of adamantane and
diamantane subunits directly connected by an oxygen atom were prepared. In addition to
classical synthesis in solution/melt, mechanochemical synthesis was also carried out, which
showed numerous advantages compared to classical synthesis. The self-organization of the
newly prepared compounds in 2D and 3D space was investigated using the technique of
scanning tunneling microscopy, the technique of helium nanodroplets and the technique of
single crystal X-ray diffraction. Ordered self-assembly of diamondoid ethers was observed,
whereby the manner of self-organization was a consequence of the initial geometrical
structures of the investigated molecules and the process was governed by spatial
intermolecular interactions. For additional characterization of the formed surface layers,
computational analysis was used in order to clarify the influence of oxygen atoms on the
orientation of molecules with respect to the surface, while London dispersion interactions
between diamondoid cages were confirmed as a driving force for the self-organization of the
adsorbed molecules. X-ray diffraction and differential scanning calorimetry analyses
confirmed the existence of phase transformations of diamondoid ethers in the solid state.

• Keywords: čvrsto stanje; diamantoidni eteri; helijeve nanokapljice; Londonove disperzijske interakcije; mehanokemijska sinteza; pretražna tunelirajuća mikroskopija
• Keywords (english): diamondoid ethers; helium nanodroplets; London dispersion interactions; mechanochemical synthesis; solid state; scanning tunneling microscopy
• Language: croatian
• URN:NBN: urn:nbn:hr:217:525561
• Promotion: 2023
• 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: 206 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2024-01-27
• Created on: 2023-02-06 11:43:14