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The incorporation of thiazyl radicals into metal-organic compounds
Thesis (MSc)--Stellenbosch University, 2023.
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| Format: | Thesis |
| Language: | en_ZA en_ZA |
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Stellenbosch : Stellenbosch University
2023
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| _version_ | 1867613851391885312 |
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| access_status_str | Open Access |
| author | Zitha, Marvin |
| author2 | Haynes, Delia |
| author_browse | Haynes, Delia Zitha, Marvin |
| author_facet | Haynes, Delia Zitha, Marvin |
| author_sort | Zitha, Marvin |
| collection | Thesis |
| dc_rights_str_mv | Stellenbosch University |
| description | Thesis (MSc)--Stellenbosch University, 2023. |
| format | Thesis |
| id | oai:scholar.sun.ac.za:10019.1/127313 |
| institution | Stellenbosch University (South Africa) |
| language | en_ZA en_ZA |
| last_indexed | 2026-06-10T12:42:41.823Z |
| license_str | Other — see source repository |
| provenance_str_mv | Harvested via OAI-PMH from SUNScholar — Stellenbosch University Repository |
| publishDate | 2023 |
| publishDateRange | 2023 |
| publishDateSort | 2023 |
| publisher | Stellenbosch : Stellenbosch University |
| publisherStr | Stellenbosch : Stellenbosch University |
| record_format | dspace |
| source_str | SUNScholar — Stellenbosch University Repository |
| spelling | oai:scholar.sun.ac.za:10019.1/127313 The incorporation of thiazyl radicals into metal-organic compounds Zitha, Marvin Haynes, Delia Stellenbosch University. Faculty of Science. Dept. of Chemistry and Polymer Science. Polymerization Compounds, Chemical Coordination compounds Radicals (Chemistry) Thesis (MSc)--Stellenbosch University, 2023. ENGLISH ABSTRACT: In this study, the incorporation of thiazyl radicals into metal-organic compounds was investigated. Previously in our group, a novel coordination polymer was isolated from the reaction of cobalt(II) meso-tetraphenylporphyrin (CoTPP) and 4-(4'-pyridyl)- 1,2,3,5-dithiadiazolyl (p-PyrDTDA). Our initial aim was to expand this study by synthesizing and investigating the coordination of other thiazyl radicals to various metalloporphyrins. 5-Methylbenzodithiazolyl (MBDTA) radical was synthesized and investigated first. A series of crystallization reactions were carried out between the MBDTA and four metalloporphyrins; CoTPP, CuTPP, NiTPP, and ZnTPP (TPP=tetraphenylporphyrin). Unfortunately, this did not yield any crystals. However, the ultraviolet-visible (UV-Vis) spectroscopic analysis of the reaction solutions, and the solid materials isolated from these reactions, revealed that coordination only occurs between CoTPP and MBDTA. Electron paramagnetic resonance (EPR) studies between CoTPP and the MBDTA also confirmed spin-pairing between the cobalt ion unpaired electron and the radical. The study was then extended to investigate the coordination of other 1,2,3,5- dithiadiazolyl radicals to metalloporphyrins. Attempts were made to synthesize and isolate zinc porphyrin-dithiadiazolyl complexes first observed by van Laeren during UV-Vis spectrophotometric titration of ZnTPP with PhDTDA or pPyrDTDA in dimethyl sulfoxide:dichloromethane. However, it was found that the coordination observed during the UV-Vis studies was caused by the formation of a zinc porphyrin-dimethyl sulfoxide complex in solution. Coordination between all four investigated 1,2,3,5-dithiadiazolyl radicals, p-PyrDTDA,4-phenyl-1,2,3,5-dithiadiazolyl (PhDTDA), 4-(3ʹ-cyanophenyl)-1,2,3,5-dithiadiazolyl (m-NCPDTDA), and 4-(4ʹcyanophenyl)-1,2,3,5-dithiadiazolyl (p-NCPhDTDA) with ZnTPP in the absence of dimethyl sulfoxide showed no evidence of coordination. However, CoTPPdithiadiazolyl associations were observed for all four dithiadiazolyl radicals. EPR titration studies between CoTPP and the dithiadiazolyl radicals also confirm a spinpairing between the spin-active materials. The last part of this study focused on investigating the inclusion of PhDTDA into cobaltcontaining MOFs. The crystal structure of an inclusion compound containing monomeric PhDTDA inside the cavity of [Co2(bpep)(obc)2], where bpeb=1,4-bis[2-(4-pyrdyl)ethenyl]benzene and obc=4,4'-oxybisbenzoate, was determined by single crystal X-ray diffraction. Thermogravimetric studies of this inclusion compound confirmed the presence of one PhDTDA molecule per unit of MOF. Overall, this study contributes to the understanding of the coordination chemistry of thiazyl radicals and metalated tetraphenylporphyrins. The inclusion of PhDTDA radical into a [Co2(bpep)(obc)2] showed promising results with the possibility of further investigations. In hierdie studie is die inkorporering van tiasielradikale in metaal-organiese verbindings ondersoek. Voorheen in ons groep is 'n nuwe koördinasie-polimeer geïsoleer deur die reaksie van kobalt(II) meso-tetrafenielporfirien (CoTPP) en 4-(4'- pyridyl)-1,2,3,5-ditiadiazoliel (p-PyrDTDA). Ons aanvanklike doel was om hierdie studie uit te brei deur ander metaal-organiese verbindings te sintetiseer deur die koördinasie van verskeie tiasielradikale na verskillende metalloporfiriene en die nuwe reeks verbindings te ondersoek. 5-metielbenzoditiazoliel (MBDTA) radikaal was eers gesintetiseer en ondersoek. 'n Reeks kristallisasiereaksies is tussen die MBDTA en vier metalloporfiriene uitgevoer naamliks: CoTPP, CuTPP, NiTPP en ZnTPP (TPP= tetrafenielporfirien). Ongelukkig het dit geen kristalle opgelewer nie. Die ultravioletsigbare (UV-Vis) spektroskopiese analise van die reaksieoplossings, en die soliede materiale wat uit hierdie reaksies geïsoleer is, het egter aan die lig gebring dat koördinasie slegs tussen CoTPP en MBDTA plaasvind. Elektronparamagnetiese resonansie (EPR) studies tussen CoTPP en die MBDTA het ook spinpairing tussen die kobaltioon se ongepaarde elektron en die radikale bevestig. Die studie is daarna uitgebrei om die koördinasie van ander 1,2,3,5-ditiadiazoliel radikale na metalloporfiriene te ondersoek. Verskeie pogings was aangewend om sinkporfyrien-ditiadiazolielkomplekse, wat voorheen vir die eerste keer deur van Laeren waargeneem is, te sintetiseer en te isoleer tydens UV-Vis spektrofotometriese titrasie van ZnTPP met PhDTDA of p-PyrDTDA in `n dimetielsulfoksied en dichloormetaan oplossing. Daar is egter gevind dat die koördinasie wat tydens die UVVis-studies waargeneem is, deur die vorming van 'n sinkporfyriendimetielsulfoksiedkompleks in oplossing veroorsaak. Koördinasie tussen al vier ondersoek 1,2,3,5-dithiadiazolyl radikale, p-PyrDTDA,4-feniel-1,2,3,5-dithiadiazolyl (PhDTDA), 4-(3ʹ-sianofeniel)-1,2,3,5-dithiadiazolyl (m-NCPDTDA) en 4-(4ʹsianofeniel)-1,2,3,5-dithiadiazolyl (p-NCPhDTDA) met ZnTPP in die afwesigheid van dimetielsulfoksied het geen bewyse van koördinasie getoon nie. Koördinasie tussen al vier ondersoek 1,2,3,5-dithiadiazolyl radikale, p-PyrDTDA,4-feniel-1,2,3,5- dithiadiazolyl (PhDTDA), 4-(3ʹ-sianofeniel)-1,2,3,5-dithiadiazolyl (m-NCPDTDA) en 4- (4ʹ-sianofeniel)-1,2,3,5-dithiadiazolyl (p-NCPhDTDA) met ZnTPP in die afwesigheid van dimetielsulfoksied het geen bewyse van koördinasie getoon nie. Die laaste deel van hierdie studie het gefokus op die ondersoek na die insluiting van PhDTDA in kobaltbevattende MOF's. Die kristalstruktuur van 'n insluitingsverbinding wat monomere PhDTDA bevat in die holte van [Co2(bpep)(obc)2], waar bpeb=1,4- bis[2-(4-pyrdyl)ethenyl]benseen en obc=4,4'-oxybisbenzoate is, was bepaal deur enkelkristal X-straaldiffraksie. Termogravimetriese studies van hierdie insluitingsverbinding het die teenwoordigheid van een PhDTDA-molekule per eenheid MOF bevestig. Oor die algemeen dra hierdie studie by tot die begrip van die koördinasiechemie van tiasielradikale en gemetalliserde tetrafenielporfiriene. Die insluiting van die PhDTDAradikaal in [Co2(bpep)(obc)2] het belowende resultate getoon met die moontlikheid van verdere ondersoeke. Masters 2023-03-02T18:17:57Z 2023-05-18T07:15:33Z 2023-03-02T18:17:57Z 2023-05-18T07:15:33Z 2023-03 Thesis http://hdl.handle.net/10019.1/127313 en_ZA en_ZA Stellenbosch University x, 114 pages : illustrations. application/octet-stream application/pdf Stellenbosch : Stellenbosch University |
| spellingShingle | Polymerization Compounds, Chemical Coordination compounds Radicals (Chemistry) Zitha, Marvin The incorporation of thiazyl radicals into metal-organic compounds |
| title | The incorporation of thiazyl radicals into metal-organic compounds |
| title_full | The incorporation of thiazyl radicals into metal-organic compounds |
| title_fullStr | The incorporation of thiazyl radicals into metal-organic compounds |
| title_full_unstemmed | The incorporation of thiazyl radicals into metal-organic compounds |
| title_short | The incorporation of thiazyl radicals into metal-organic compounds |
| title_sort | incorporation of thiazyl radicals into metal organic compounds |
| topic | Polymerization Compounds, Chemical Coordination compounds Radicals (Chemistry) |
| url | http://hdl.handle.net/10019.1/127313 |
| work_keys_str_mv | AT zithamarvin theincorporationofthiazylradicalsintometalorganiccompounds AT zithamarvin incorporationofthiazylradicalsintometalorganiccompounds |