Svojstva homo- i heterometalnih kompleksnih spojeva priređenih iz tris(oksalatnih) i tris(kloranilatnih) građevnih blokova

doctoral thesis

• Title (english): Properties of homo- and heterometallic complexes prepared using tris(oxalato) and tris(chloranilato) building blocks
• Author: Lidija Kanižaj
• Mentor: Marijana Jurić (mentor)
• Committee member: Željka Soldin (predsjednik povjerenstva)
• Committee member: Jasminka Popović (član povjerenstva)
• Committee member: Lidija Androš Dubraja (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2020-11-19, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

Istražene su reakcije građevnog bloka A3[ML3]·3H2O {A = K+, NH4+ ili [(C4H9)4N)4]+; M = Cr3+ ili Fe3+; L = C2O42– ili C6O4Cl22–}, bakrove(II) soli i N-donorskog liganda (imidazola, 2,2'-bipiridina, 1,10-fenantrolina ili 2,2':6',2''-terpiridina), uz dodatak tetraklorkinona i KI u nekim reakcijama, tehnikom nadslojavanja ili u hidrotermalnim uvjetima. Priređen je 51 novi spoj: 35 oksalatnih, od čega je 29 heterometalnih (19 [CuIICrIII] i 10 [CuIIFeII/III]), i 12 kloranilatnih, od čega je 7 heterometalnih (4 [CuIICrIII] i 3 [CuIIFeIII]). Pripravljeno je 9 kompleksa s mononuklearnim, 11 s dinuklearnim, 5 s trinuklearnim, 2 s tetranuklearnim i 1 s heksanuklearnim jedinkama. Priređeno je i 13 jednodimenzijskih te 6 trodimenzijskih koordinacijskih polimera. Svi su spojevi okarakterizirani IR spektroskopijom, te su im određene molekulske i kristalne strukture. Za 15 spojeva su njihova svojstva ispitana metodama termičke analize te magnetska svojstva za 14 spojeva koji sadrže premošćujuću oksalatnu skupinu, odnosno električna svojstva za 7 spojeva. 5 heterometalnih oksalatnih kompleksa je proučavano u obliku molekulskih prekursora za dobivanje mješovitih metalnih oksida termičkom razgradnjom; dobivenom jednofaznom sustavu CuCrO2 istražena je fotokatalitička aktivnost u reakciji cijepanja vode. Kod 2 spoja je uočen fotokromizam, odnosno termokromizam kod 1.

Abstract (english)

The reactions of building block A3[ML3]·3H2O {A = K+, NH4+ or [(C4H9)4N)4]+; M = Cr3+ or Fe3+; L = C2O42– or C6O4Cl22–}, copper(II) salt and N-donor ligand (imidazole, 2,2'-bipyridine, 1,10-phenanthroline or 2,2':6',2"-terpyridine), with the addition of tetrachloroquinone and KI in some reactions were studied, in layering technique or in hydrothermal conditions. 51 new compounds were prepared: 35 oxalate-based {29 heterometallic [19 (CuIICrIII) and 10 (CuIIFeII/III)]}, and 12 chloranilate {7 heterometallic [4 (CuIICrIII) and 3 [CuIIFeIII]} were isolated. In these reactions 9 complexes with mononuclear, 11 with dinuclear, 5 with trinuclear, 2 with tetranuclear and 1 with hexanuclear units were obtained. 13 one-dimensional and 6 three-dimensional coordination polymers were formed. IR and structural characterization was done for all the complexes. For 15 compounds thermal properties were investigated, for 14 compounds with bridging oxalate group magnetic properties, and for 7 compounds electric properties were studied. 5 selected heterometallic oxalate complexes were tested as molecular precursors for mixed-metal oxides and single-phased CuCrO2 was obtained. Its photocatalytic activity in water splitting reaction was tested. 2 compounds showed photochromism and 1 thermochromism.

• Keywords: IR-spektroskopija; mješoviti metalni oksidi; molekulska struktura; kristalna struktura; molekulski prekursori; TG-analiza; DTA-analiza; tris(oksalato) građevni blokovi; tris(kloranilato) građevni blokovi
• Keywords (english): building blocks; chloranilate group; mixed-metal oxides; oxalate group; IR spectroscopy; TG-analysis; DTA analysis
• Language: croatian
• URN:NBN: urn:nbn:hr:217:279566
• Promotion: 2020
• 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: 251 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2022-11-19
• Created on: 2020-12-11 09:42:00