Preparation and coordination chemistry of bis-pyridyl diamide ligands

Batisai, Eustina (2010-03)

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2010.

Thesis

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.

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