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Preparation and coordination chemistry of bis-pyridyl diamide ligands

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT:
The number of coordination complexes utilizing bis-pyridyl diamide ligands has increased
significantly over the past decade. This is attributed to the relatively easy synthetic procedure
of the ligands and interesting structural features such as helicity, water clusters and porosity
that the coordination complexes possess. In the first part of this study, the following eight
structurally related bis-pyridyl diamide ligands:
• N,N'-bis(pyridin-4-ylmethyl)isophthalamide (ISO);
• N,N'-bis(pyridyl-4-ylmethyl)terephthalamide (TER);
• N,N'-bis(pyridin-4-ylmethyl)hexanediamide (ADI);
• N,N'-bis(pyridin-4-ylmethyl)butanediamide (SUC);
• N,N'-bis(pyridin-4-ylmethyl)biphenyl-4,4'-dicarbonyl dicarboxamide (DIP);
• N,N'-dipyridin-2-ylpentanediamide (GLUT);
• (2E)-N,N'-bis(2-pyridin-4-ylmethyl)but-2-enediamide (FUM);
• 4-(pyridin-4-ylmethyl)aminocarbonyl benzoic acid (TER-A).
were synthesized and characterized by NMR, FTIR, MS and SCD. In the second part, the
synthesized ligands were reacted with a variety of transition metal salts to yield fifteen novel
coordination polymers and one discrete complex. SCD analysis showed that of the sixteen
complexes thirteen formed 1-D chains, two formed 2-D networks, and one formed a discrete
unit. Hydrogen bonding interactions between water molecules, the counterions and the amide
groups resulted in connection of the lower dimension entities into higher dimension networks.
The synthesized ligands were co-crystallized with trimesic acid and a novel co-crystal
consisting of ADI and trimesic acid was obtained. SCD analysis showed that the co-crystal
featured the amide homosynthon as well as the pyridine/carboxylic acid heterosynthon. / AFRIKAANSE OPSOMMING:
Die aantal koördinasie komplekse met dipiridieldiamied ligande het noemenswaardig
vermeerder oor die afgelope dekade. Hierdie groei kan toegeskryf word aan die eenvoudige
sintetiese prosedure en interessante strukturele eienskappe van dié koördinasie komplekse, wat
o.a. helikse, waterbondels en poreuse materiale vorm. In die eerste deel van hierdie studie is
die agt onderstaande struktureel verwante dipiridieldiamied ligande se sintese en
karakterisering deur kernmagnetieseresonansie, Fourier transform infrarooi,
massaspektrometrie en enkel kristal X-straal diffraksie (SCD) beskryf:
• N,N'-bis(piridien-4-ielmetiel)isoftalamied (ISO);
• N,N'-bis(piridien-4-ielmetiel)tereftalamied (TER);
• N,N'-bis(piridien-4-ielmetiel)heksaandiamied (ADI);
• N,N'-bis(piridien-4-ielmetiel)butaandiamied (SUC);
• N,N'-bis(piridien-4-ielmetiel)bifeniel-4,4'-dikarbonieldikarboksamied (DIP);
• N,N'-dipiridien-2-ielpentaandiamied (GLUT);
• (2E)-N,N'-bis(2-piridien-4-ielmetiel)but-2-eendiamied (FUM);
• 4-(piridien-4-ielmetiel)aminokarboniel bensoësuur (TER-A).
In die tweede gedeelte is bg. ligande met 'n reeks oorgangsmetaalsoute gereageer om vyftien
nuwe koördinasiepolimere, asook een diskrete kompleks, te lewer. SCD analise toon dat van
hierdie sestien komplekse vorm dertien 1-D kettings, twee vorm 2-D netwerke en slegs een
vorm 'n diskrete eenheid. Waterstofbindings tussen die water molekules, die teen-ione en die
amied groepe het laer dimensie (1-D) eenhede verbind om hoër dimensionele netwerke (2-D)
te vorm. Mede-kristallisasie van die gesintetiseerde ligande met trimesielsuur het 'n nuwe
mede-kristal tussen ADI en triemesielsuur opgelewer. Enkelkristal diffraksie toon dat die
mede-kristal beide die amied homosinton en die piridien/karboksielsuur heterosinton bevat.

Identiferoai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:sun/oai:scholar.sun.ac.za:10019.1/4128
Date03 1900
CreatorsBatisai, Eustina
ContributorsBarbour, L. J., Le Roex, T., University of Stellenbosch. Faculty of Science. Dept. of Chemistry and Polymer Science.
PublisherStellenbosch : University of Stellenbosch
Source SetsSouth African National ETD Portal
LanguageEnglish
Detected LanguageEnglish
TypeThesis
RightsUniversity of Stellenbosch

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