Održivost motiva halogenske veze pri kokristalizaciji amina, imina i njihovih koordinacijskih spojeva s perhalogeniranim aromatima

doctoral thesis

• Title (english): Sustainability of halogen bond motifs in the cocrystallization of amines, imines and their coordination compounds with perhalogenated aromates
• Author: Vinko Nemec
• Mentor: Dominik Cinčić (mentor)
• Committee member: Višnja Vrdoljak (predsjednik povjerenstva)
• Committee member: Ivana Biljan (član povjerenstva)
• Committee member: Krešimir Molčanov (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2019-05-24, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

Mehanokemijskom sintezom uz prisutnost tekućine istraživana je mogućnost kokristalizacije
amina, imina i koordinacijskih spojeva s perhalogeniranim aromatskim spojevima, te su
pripravljena 82 nova spoja. Od toga su metodama kristalizacije iz otopine dobivena 24 jedinična
kristala. Dobiveni produkti okarakterizirani su difrakcijom rentgenskog zračenja u
polikristalnom uzorku i jediničnom kristalu, te metodama termičke analize. Strukturnom
analizom pokazano je da je halogenska veza dominanta međumolekulska interakcija u
kokristalima. Utvrđeno je da su kisikovi atomi karbonilne skupine i morfolinskog fragmenta
dobri akceptori halogenske veze X∙∙∙O (X = I, Br), te da postoji održivost navedenog motiva od
amina prema većim građevnim blokovima. Temeljem halogenske veze s karbonilnim kisikovim
atomom pripravljeno je osam kokristala koordinacijskih spojeva bakra(II) i nikla(II) s donorima
koji sadrže brom i jod. Pokazano je da se korištenjem donora različite topičnosti, jakosti i
geometrije može ugađati supramolekulsku arhitekturu i termičku stabilnost produkata.

Abstract (english)

Eighty-two new compounds were synthesized by liquid-assisted grinding amines, imines and
coordination compounds with perhalogenated aromatic compounds, followed by the
preparation of 24 single crystals via solution-based crystallization methods. The obtained
products were characterized by powder and single crystal X-ray diffraction, and by thermal
analysis methods. Structural analysis of the cocrystals shows that the dominant supramolecular
interaction is the halogen bond. It also demonstrates that carbonyl and morpholinyl oxygen
atoms are good acceptors of X∙∙∙O (X = I, Br) halogen bonds, and that these motifs show
sustainability in the series from amines to bigger building blocks. Utilizing the halogen bond
motif with the carbonyl oxygen atom, four donors containing iodine or bromine atoms have
been cocrystallized with square planar copper(II) and nickel(II) coordination compounds. It is
also shown that product supramolecular architectures and thermal stabilities can be altered via
utilizing donors of different geometries, strengths, and topicities.

• Keywords: halogenska veza; kokristali; kristalizacija; kristalno inženjerstvo; mehanokemijska sinteza
• Keywords (english): cocrystals; crystal engineering; crystallization; halogen bond; mechanochemical synthesis
• Language: croatian
• URN:NBN: urn:nbn:hr:217:197439
• 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: 357 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access
• Created on: 2019-06-03 12:47:19