Tetraedarski koordinacijski spojevi vrste CoX2L (X = Cl, Br i I) kao akceptori halogenske veze u metaloorganskim kokristalima

master's thesis

• Title (english): Tetrahedral coordination compounds CoX2L (X=Cl, Br and I) as halogen bond acceptors in metal-organic cocrystals
• Author: Laura Čehulić
• Mentor: Dominik Cinčić (mentor)
• Committee member: Dominik Cinčić (predsjednik povjerenstva)
• Committee member: Iva Juranović Cindrić (član povjerenstva)
• Committee member: Đani Škalamera (član povjerenstva)
• Committee member: Vladimir Stilinović (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2023-02-13, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U ovom diplomskom radu ispitana je mogućnost kokristalizacije koordinacijskih spojeva vrste
CoX2L (gdje je X = Cl, Br ili I, a L = 6,6'-dimetil-2,2'-bipiridin) i perhalogeniranih donora
halogenske veze, s ciljem izučavanja mogućnosti nastajanja kokristala s metaloorganskom
podjedinicom te uspoređivanja akceptorskog potencijala halogenidnih iona koordiniranih na
metalni centar za ostvarivanje halogenske veze. Mehanokemijskom sintezom i kristalizacijom
iz otopine priređeno je sedam novih kokristala koji su okarakterizirani difrakcijom
rendgenskoga zračenja na praškastom uzorku, difrakcijom rendgenskoga zračenja u jediničnom
kristalu i termogravimetrijskom analizom. U svim strukturno okarakteriziranim kokristalima
utvrđeno je kako je halogenska veza Co−X···I (X = Cl, Br ili I) dominantna međumolekulska
interakcija koja se ostvaruje između atoma joda perhalogeniranog spoja kao donora halogenske
veze i halogenidnog liganda koordinacijskog spoja kobalta(II) kao akceptora halogenske veze.
Pokazano je i da se korištenjem perhalogeniranih donora različite topičnosti i geometrije može
ugađati supramolekulska arhitektura i termička stabilnost dobivenih produkata.

Abstract (english)

Within this master thesis, the possibility of cocrystallization of coordination compound CoX2L
(X = Cl, Br or I, L = 6,6'-dimethyl-2,2'-bipyridine) and perhalogenated halogen bond donors
was examined, with the aim of studying the plausibility of cocrystal formation with a metalorganic subunit and comparing the ability of the halide ions coordinated to the Co(II) metal
center to act as a halogen bond acceptor. Seven new cocrystals were synthesized by
mechanochemical synthesis and crystallization from solution. The obtained products were
characterized by powder and single crystal X-ray diffraction, and by thermogravimetric
analysis. Structural analysis of the cocrystals revealed that the dominant supramolecular
interactions are Co−X···I halogen bonds (X = Cl, Br or I) formed between the iodine atom of
the halogen bond donor and the halogen ligand of the cobalt(II) coordination compound as a
halogen bond acceptor. The results of this study also demonstrate the possibility of altering
supramolecular architectures and thermal stabilities of the products by utilizing donors
featuring different geometries 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:217:182428
• Project: Number: IP-2019-04-1868; Title: Nove građevne jedinke u supramolekulskom dizajnu složenih višekomponentnih molekulskih kristala temeljenih na halogenskim vezama; Title: New building blocks for the supramolecular design of complex multi-component molecular crystals based on halogen bonds; Acronym: HaloBond; Leader: Dominik Cinčić; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: IP
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2024-02-13
• Created on: 2023-02-16 14:34:10