Utjecaj acetilacetonatnih supstituenata na koordinaciju i supramolekulsko povezivanje amidnih koordinacijskih spojeva bakra(II)

master's thesis

• Title (english): Impact of acetylacetonate substituents on coordination and supramolecular conectivity in the amide coordination compounds of copper(II)
• Author: Ingrid Gregorović
• Mentor: Marijana Đaković (mentor)
• Committee member: Marijana Đaković (predsjednik povjerenstva)
• Committee member: Vesna Petrović Peroković (član povjerenstva)
• Committee member: Sanda Rončević (član povjerenstva)
• Committee member: Željka Soldin (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2018-09-21, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U sklopu ovog rada priređeni su heksafluoracetilacetilacetonatni i trifluoracetilacetilacetonatni kooordinacijski spojevi bakra(II) s pirazinamidom, nikotinamidom i izonikotinamidom, [Cu(hfac)2(pza)2] (1a), [Cu(hfac)2(nia)2] (1b), [Cu(tfac)2(pza)]MeOH (2a), [Cu(tfac)2(nia)2] (2b) i [Cu(tfac)2(isa)] (2c). Svi spojevi pripravljeni su otopinskom sintezom pri sobnoj temperaturi te mehanokemijskom sintezom uz dodatak katalitičke količine otapala (LAG). Dobiveni produkti okarakterizirani su difrakcijom rentgenskog zračenja u polikristalnom uzorku (PXRD) te spektroskopskim (IR) i termičkim (TGA/DTA i DCS) metodma. Svim spojevima određena je molekulska i kristalna stuktura difrakcijom rentgenskog zračenja u jediničnom kristalu (SCXRD).
Ustanovljeno je da heksafluoracetilacetonatni spojevi bakra(II) (1a, 1b) čine spojeve oktaedarske koordinacije neovisno o vezanom heterocikličkom ligandu. U slučaju s trifluoracetilacetonatnih spojeva bakra(II) (2a, 2c) ustanovljeno je da preferirano nastaju pentakoordinirani spojevi kvadratno-piramidalne geometrije, osim u slučaju nikotinamida (2b) kada nastaje spoj oktaedarske koordinacije.
Analizom supramolekulskih interakcija u kristalnim stukturama priređenih spojeva uočeno je da je u slučaju nikotinamidnih spojeva (1b, 2b) amidni supramolekulski motiv lanca, C(4), uspješno prenesen iz organske u metalo-organsku sredinu, dok je supramolekulski amidni motiv prstena uočen kod trifluoracetilacetonatnog koordinacijskog spoja bakra(II) s pirazinamidom (2a).

Abstract (english)

This diploma thesis presents synthesis of hexafluoro- and trifluoroacetylacetonate complexes of copper(II) with pyrazinamide, nicotinamide and isonicotinamide, namely [Cu(hfac)2(pza)2] (1a), [Cu(hfac)2(nia)2] (1b), [Cu(tfac)2(pza)]MeOH (2a), [Cu(tfac)2(nia)2] (2b) i [Cu(tfac)2(isa)] (2c). The complexes were prepared via two synthetic routes, solution synthesis at room temperature and liquid-assisted mechanochemical grinding (LAG). The products were characterized by powder X-ray diffraction (PXRD), as well as spectroscopic (IR) and thermal (TGA/DTA and DSC) methods. The crystal structures of all compound were determined by single-crystal X-ray diffration (SCXRD).
Octahedral coordination geometry has regularly been observed for hexafluoroacetylacetonato copper(II) complexes (1a, 1b) regardless of the heterocyclic ligand used, while for trifluoroacetylacetonato copper(II) complexes (2a, 2c), pentacoordnation with square-pyrimidal geometry was preffered. The only exception was the trifluoroacetylacetonato copper(II) complex with nicotinamide (2b) where the octahedral geometry was established.
Analysis of supramolecular interactions showed that the amide catemeric motif C(4) was successfully transferred from organic to metalo-organic environment for all nicotinamide complexes (1b, 2b), while the amide ring motif has been observed for triflouroacetilacetonate complexes of copper(II) with pyrazinamide (2a).

• Keywords: koordinacijski spojevi bakra (II); pirazinamid; nikotinamid; izonikotinamid; heksafluoroacetilaecton; trifluoroacetilaceton; supramolekulski amidni sintoni
• Keywords (english): coordination compounds of copper (II); pyrazinamide; nicotinamide; isonicotinamide; hexafluoroacetylacetonate; trifluoroacetylacetonate; supramolecular amide synthons
• Language: croatian
• URN:NBN: urn:nbn:hr:217:322697
• 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: 2020-09-21
• Created on: 2018-11-19 13:39:12