Koordinacijski spojevi kobalta(II) s halogenidnim ligandima kao akceptorima halogenske veze

master's thesis

• Title (english): Cobalt(II) coordination compounds with halide ligands as halogen bond acceptors
• Author: Vedran Dubravec
• Mentor: Dominik Cinčić (mentor)
• Committee member: Dominik Cinčić (predsjednik povjerenstva)
• Committee member: Sanda Rončević (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: 2023-02-17, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U ovom diplomskom radu sintetizirana su tri koordinacijska spoja kobalta(II) korištena kao
akceptori halogenske veze – dikloro-, dibromo- i dijodo-(6,6´´-dibrom-2,2´:6´,2´´-
terpiridin)kobalt(II). Koordinacijski spojevi kokristalizirani su s odabranim perfluoriranim
jodbenzenskim spojevima kao donorima halogenske veze s ciljem usporedbe potencijala
halogenog liganda kao akceptora halogenske veze Co–X∙∙∙I (X = Cl, Br, I) kao i izučavanja
utjecaja bromovih atoma na periferiji terpiridinskog liganda na ostvarivanje halogenskih veza,
kao i njihov akceptorski potencijal. Sinteza koordinacijskih spojeva i kokristala provedena je
mehanokemijski, dok su jedinični kristali dobiveni kristalizacijom iz otopine.
Mehanokemijskom sintezom ukupno je dobiveno osam novih kristalnih produkata koji su
okarakterizirani difrakcijom rendgenskog zračenja na praškastom uzorku. Za one produkte čiji
su jedinični kristali uspješno priređeni dodatno su okarakterizirani difrakcijom rendgenskog
zračenja u jediničnom kristalu i termogravimetrijskom analizom. Strukturnom analizom
kokristala utvrđeno je kako je dominantna međumolekulska interakcija Co–X∙∙∙I (X = Cl, Br,
I). Atomi broma na periferiji liganda sudjeluju u kontaktima Br∙∙∙H, dok samo u jednom
kokristalu ostvaruju halogenske veze Co–Br∙∙∙Br i Br∙∙∙I u kojima sudjeluju kao donori i kao
akceptori.

Abstract (english)

In this diploma thesis three cobalt(II) coordination compounds were synthesized and used as
halogen bond acceptors – dichloro-, dibromo-, and diiodo-(6,6"-dibromo-2,2':6',2'-
terpyridine)cobalt(II). Coordination compounds were cocrystallized with selected
perfluorinated iodobenzene compounds as halogen bond donors in order to compare the
potential for halogen bonding of the halogen atoms located peripherally on the terpyridine
ligands, as well as their acceptor potential. Mechanochemical methods were used to synthesize
bulk coordination compounds and cocrystals, whereas crystallization from solution was used to
obtain single crystals. Mechanochemical synthesis resulted in eight new crystalline phases
which were then identified using X-ray powder diffraction. The products were also
characterized by thermogravimetric analysis and single crystal X-ray diffraction in cases where
single crystals were successfully obtained. Structural analysis of the compounds revealed that
the dominant intermolecular interaction is Co–X∙∙∙I (X = halogen). The bromine atoms on the
ligand's periphery participate in Br∙∙∙H contacts, but in one cocrystal they participate in the
halogen bonds Co–Br∙∙∙Br and Br∙∙∙I, where they act as both acceptors and donors.

• Keywords: halogenska veza; kokristali; koordinacijski spojevi; mehanokemijska sinteza
• Keywords (english): cocrystals; coordination compounds; halogen bond; mechanochemical synthesis
• Language: croatian
• URN:NBN: urn:nbn:hr:217:893123
• 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: 2024-02-17
• Created on: 2023-02-22 13:30:38